WO2009074321A1 - Activation rapide d'un précurseur d'agent tensio-actif - Google Patents

Activation rapide d'un précurseur d'agent tensio-actif Download PDF

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WO2009074321A1
WO2009074321A1 PCT/EP2008/010536 EP2008010536W WO2009074321A1 WO 2009074321 A1 WO2009074321 A1 WO 2009074321A1 EP 2008010536 W EP2008010536 W EP 2008010536W WO 2009074321 A1 WO2009074321 A1 WO 2009074321A1
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Prior art keywords
surfactant
surfactant precursor
water
precursor
chz
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Seyed Reza Younesi
Martin Andersson
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YKI Ytemiska Institutet AB
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YKI Ytemiska Institutet AB
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
    • C07D305/12—Beta-lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising

Definitions

  • the present invention relates to a method for rapid activation of a surfactant precursor, having the general formula I
  • the invention further relates to compositions for rapid activation of the surfactant precursor and to the use of such compositions.
  • cleavable surfactants So-called cleavable surfactants have been known for several years and the different classes of such surfactants have been nicely reviewed by Stjerndahl et al. in "Cleavable Surfactants, Novel Surfactants - Preparation, Applications, and Biodegradability", 2 ed., Holmberg ed., Marcel Dekker, Inc., USA, 2003.
  • a main reason for the development of cleavable surfactants has been environmental concern and a desire for biodegradable surfactants.
  • the main types of cleavable surfactants known today are: 1 ) Surfactants labile at acidic conditions
  • Thermolabile surfactants According to Stjerndahl, most cleavable surfactants contain a hydrolysable bond and thus belong to type 1 or 2. For these surfactants, a change of pH is needed to initiate cleaving of the surfactant.
  • the degradation product is often a soap or a long-chain alcohol, of which at least the former is clearly surface active. Thus, the cleaving of these compounds does not automatically imply that surface activity is lost.
  • surfactant In the case of light sensitive surfactants (type 3), the surfactant has to be exposed to light for a certain amount of time to obtain the desired cleaving.
  • surfactants that decompose in contact with specific chemicals (type 4), e.g. ozone cleavable surfactants, are used in specific applications only.
  • thermolabile surfactants type 5
  • the decomposition rate is intended to be controlled by regulation of the temperature.
  • Hayashi et al. (JAOCS 62(3):555-557 (1985)) report preparation of amine oxide surfactants by oxidation of 2-alkoxy-N,N-dimethylethylamines with hydrogen peroxide.
  • the 2-alkoxy-N,N-dimethylethylamine N-oxide surfactants formed were good foam stabilizers and stable up to 100 0 C, but decomposed rapidly to vinyl ethers at 150 °C. Hence, the decomposition temperature of these surfactants is not compatible with use in aqueous compositions.
  • GB 923,449 discloses that unsaturated polymerisable compounds can be advantageously polymerised in aqueous medium and in the presence of dispersing agents and activators by using as a dispersing agent a salt of a partial ester of an aliphatic polycarboxylic acid with one or more alcohols having 3 to 20 carbon atoms and heating the resultant polymer emulsion at temperatures between 60 and 200 0 C.
  • dispersing agents have the drawback of being intrinsically sensitive to alkaline and acidic conditions, causing premature degradation of the surfactant under such conditions.
  • cleavable surfactants and dispersing agents of types 1-4 are either adapted for speciality applications only (being light sensitive or dependent on a specific substance) or cannot be utilised and cleaved at substantially constant pH conditions. Furthermore, cleaving does not always result in loss of surface activity.
  • Existing thermolabile surfactants (type 5) are not suitable in water based applications and/or under alkaline or acidic conditions.
  • AKD alkyl ketene dimers, is a group of molecules with a wide range of industrial applications. For example, AKD is used as reactive size in paper manufacture. AKD reacts with hydroxyl groups of the cellulose and provides the paper with a hydrophobic surface. This is described in Roberts, J.
  • AKD has been shown to be a useful precursor for a thermolabile surfactant.
  • hydrolysis of AKD using potassium hydroxide and dry ethanol is described as means for converting the AKD to the thermolabile surfactant.
  • this method suffers from a number of drawbacks.
  • One disadvantage of this method is that the reaction is relatively slow, which can be a problem in applications such as in detergent compositions if sufficient conversion can not be achieved within the time limits set by normal wash cycles, or within acceptable time frames for pre-activation of the surfactant precursor prior to use. Waiting times on the order of a few minutes could be acceptable for pre-activation in applications like automatic car washing, laundry, etc. Longer waiting times will make use of the surfactant precursor impractical.
  • thermolabile surfactant in order for AKD to be useful as a surfactant precursor in industrial or domestic applications, there is a need for a method providing rapid activation of AKD to the corresponding thermolabile surfactant.
  • An object of the present invention is to provide a method for rapid conversion of an alkyl ketene dimer to a deactivable thermolabile beta keto acid surfactant under conditions allowing use of said alkyl ketene dimer as a surfactant precursor in industrial and/or domestic applications.
  • Another object of the present invention is to provide a method for activation of a alkyl ketene dimer to a deactivable thermolabile beta keto acid surfactant or a salt thereof, which allows rapid preparation of the thermolabile surfactant without significant premature decomposition of the formed surfactant.
  • Another object of the present invention is to provide a method for rapid conversion of an alkyl ketene dimer to a deactivable thermolabile beta keto acid surfactant using materials with low- or non-flammable properties.
  • Yet another object of the present invention is to provide a surfactant precursor composition which may conveniently be used for rapidly obtaining a deactivable thermolabile beta keto acid surfactant.
  • the present invention provides a method of activating a surfactant precursor having the general formula I
  • R 1 and R 2 are hydrophobic moiety, resulting in the formation of a surfactant, characterized in that said activation is performed by a) providing said surfactant precursor, b) mixing the surfactant precursor with water and an alkaline compound to provide a high surface contact area between said surfactant precursor and water and alkaline compound, such that the pH of the resulting mixture is 10 or higher, c) allowing the surfactant precursor to react with said water and an alkaline compound.
  • R 1 is a hydrophobic moiety.
  • R 2 is a hydrophobic moiety.
  • R 1 and R 2 are both hydrophobic moieties.
  • R 1 and R 2 are both hydrophobic moieties of the same type.
  • the surfactant precursor may be a liquid or a solid, e.g. depending on R 1 and R 2 .
  • a typical characteristic of a surfactant precursor according to the invention is that it does not degrade or decompose rapidly at room temperature.
  • a thermolabile surfactant can be stored in the form of a thermally stable surfactant precursor according to the present invention, which can be activated to said surfactant on-site or just before use.
  • the surfactant precursor of the present invention may be activated (i.e. transformed to the surfactant) by hydrolysis, optionally followed by an adjustment of pH. Activation of the surfactant precursor of the present invention to the corresponding surfactant can be achieved by hydrolysis according to the general reaction scheme below.
  • R i -CH C CH R 2 o r R i — C u c CH R 2
  • thermolysis of AKD proceeds slowly as an undesired side reaction in aqueous dispersions under typical papermaking conditions, such as a temperature in the range of 50-90 0 C and a pH value in the range of 6-9. Under such high temperatures the thermal decomposition of the formed thermolabile surfactant will proceed quickly, resulting in formation of the corresponding keton compound. Therefore, under papermaking conditions no significant amounts of a thermolabile surfactant will be obtained. Since the surfactant precursors generally are very hydrophobic, they exhibit very low solubility in water. Aqueous compositions comprising the surfactant precursors will instead present the form of dispersions of surfactant precursor particles in an aqueous phase. In order to achieve an acceptable rate of activation of the surfactant precursor at temperatures where decomposition of the formed thermolabile surfactant is slow, the present inventors have therefore previously employed a solution of potassium hydroxide in dry ethanol for activating the surfactant precursor.
  • the present invention is based on recent research showing that addition of water to the activation reaction, even in small amounts, under certain conditions increases the rate of activation of the surfactant precursor at a scale which is highly surprising.
  • the conditions under which this surprising increase in the rate of activation is obtained include a sufficiently high contact surface between the surfactant precursor and the water as well as the presence of an alkaline compound providing a sufficiently high pH for the activation reaction to take place.
  • the activation method according to the present invention has been shown to provide an increase in the rate of activation of an alkyl ketene dimer to the corresponding surfactant on the order of 8-60 times under similar conditions in terms of temperature and pH.
  • the mixture of surfactant precursor, alkaline compound and water comprises at least 0.5 % by weight of water. In another embodiment, the mixture of surfactant precursor, alkaline compound and water comprises at least 1 % by weight of water. In another embodiment, the mixture of surfactant precursor, alkaline compound and water comprises at least 5 % by weight of water. In another embodiment, the mixture of surfactant precursor, alkaline compound and water comprises at least 10 % by weight of water. In an embodiment of the inventive method, said reaction results in the activation of at least 25 % of the surfactant precursor within 30 minutes of mixing. In another embodiment, said reaction results in the activation of at least 50 % of the surfactant precursor within 30 minutes of mixing.
  • a high contact surface area between surfactant precursor, water and alkaline compound as required to obtain the high rate of activation of the present invention may be achieved in a number of different ways.
  • High contact surface area may in one embodiment of the present invention be achieved by providing the surfactant precursor in an emulsion with water having a sufficiently low particle size. The present inventors have shown that the rate of activation increases significantly with decreasing particle size.
  • a high contact surface area between surfactant precursor, water and alkaline compound is achieved by addition of a polar organic co-solvent to the mixture.
  • a high contact surface area between the surfactant precursor and the water may be provided in a number of different ways.
  • One example of a way of achieving a high contact surface area is by providing the water and surfactant precursor in the form of a nanoemulsion.
  • Another example of a way of achieving a high contact surface area is by providing the water and surfactant precursor in the form of a mixture or a molecular solution using a suitable co-solvent.
  • water and surfactant precursor are provided in the form of an emulsion of liquid or solid particles of surfactant precursor dispersed in an aqueous phase.
  • the particles of surfactant precursor should preferably be small.
  • the average particle diameter of the surfactant precursor in said emulsion is 5 ⁇ m or less. In another embodiment, the average particle diameter of the surfactant precursor in said emulsion is 2 ⁇ m or less. In yet another embodiment, the average particle diameter of the surfactant precursor in said emulsion is 1 ⁇ m or less.
  • a nanoemulsion i.e. an emulsion in which the dispersed particles have an average diameter of 1000 nm or less, is therefore especially useful in the present invention.
  • Emulsions and nanoemulsions may optionally be stabilized using suitable surfactants.
  • suitable surfactants suitable for stabilization of an emulsion or nanoemulsion for use with the present invention include, but are not limited to, Berol OX 91-8.
  • Other examples of surfactants suitable for preparation and/or stabilization of specific emulsions or nanoemulsions may readily be identified by a person skilled in the art of surfactants and emulsions.
  • An emulsion may be prepared by any suitable method as described in the art.
  • Non-limiting examples of methods for preparing an emulsion include mechanical stirring or mixing, high shear mixing and phase inversion emulsification.
  • a nanoemulsion may be prepared by any suitable method as described in the art.
  • methods for preparing a nanoemulsion include high shear mixing and phase inversion emulsification.
  • said surfactant precursor is provided in a physical form allowing a high surface area of surfactant precursor to be brought in contact with said water and an alkaline compound.
  • said surfactant precursor is provided in the form of an emulsion.
  • Such an emulsion may for example be an emulsion or nanoemulsion of the surfactant precursor in water.
  • the surfactant precursor may be liquid or solid. If a liquid surfactant precursor is used, a high contact surface may preferably be provided in the form of an emulsion. If a solid surfactant precursor is used, a high contact surface may preferably be provided in the form of a dispersion of solid surfactant precursor particles in an aqueous phase.
  • the surfactant precursor may also be provided in solid form.
  • the surfactant precursor is provided in the form of solid particles.
  • the surfactant precursor is provided in the form of solid particles dispersed in water.
  • the average particle diameter of the solid surfactant precursor particles is 5 ⁇ m or less. In another embodiment, the average particle diameter of the solid surfactant precursor particles is 2 ⁇ m or less. In yet another embodiment, the average particle diameter of the solid surfactant precursor particles is 1 ⁇ m or less.
  • a high contact surface area between may also be achieved by the addition of a co-solvent.
  • a co-solvent for use with the invention should preferably capable of solubilizing the hydrophobic surfactant precursor and, at the same time, capable of dissolving at least a small amount of water.
  • the method of the invention may comprise addition of a polar organic co-solvent to a mixture containing the surfactant precursor.
  • Said polar organic co-solvent may preferably comprise a solvent in which both said surfactant precursor and water are at least partially soluble.
  • the properties of a co-solvent for use with the present invention should allow a sufficient amount of water to be dissolved with the surfactant precursor.
  • the co-solvent may be added directly to the surfactant precursor, but it may also be added to the water or to a mixture of the surfactant precursor and the water.
  • the polar organic co-solvent may for example be added directly to the surfactant precursor of step a), or it may be added directly to the water prior to the mixing in step b).
  • the polar organic co-solvent may also be added to the mixture obtained from step b).
  • Use of a solvent, which is capable of dissolving the surfactant precursor, at least partially, and which at the same time is polar enough to dissolve a sufficient amount of water and hydroxide ions, will allow the water and alkaline compound molecules to be brought in contact more efficiently and the activation reaction to proceed more quickly.
  • solvents suitable for use as co-solvents in accordance with the present invention include, but are not limited to, ethanol, isopropanol, Dowanol DPM (a glycol ether supplied by Dow Chemical Company) and Dowanol PnB (a glycol ether supplied by Dow Chemical Company).
  • solvents or solvent mixtures suitable for use as co-solvents with the present invention may be identified by the skilled man with the aid of the present disclosure without deviating from the spirit and scope of the present invention.
  • Non-limiting examples of polar organic co-solvents useful with the invention include methanol, ethanol, isopropanol, dipropylene glycol methyl ether, propylene glycol n-butyl ether, ethyl acetoacetate and mixtures thereof.
  • the polar organic co-solvent is ethanol. In another embodiment the polar organic co-solvent is ethyl acetoacetate.
  • the co-solvent may also be a mixture of different solvents, wherein said mixture is miscible with water or an aqueous solution, and in which the surfactant precursor is at least partially soluble.
  • the co-solvent may be a solvent which fulfils the above requirements for allowing close contact between the surfactant precursor and water and which, in addition, is capable of taking part in a neutralization reaction with the alkaline compound. If exothermic, such a neutralization reaction will provide extra heat to the activation reaction and thereby further increase the rate of activation.
  • Ethyl acetoacetate is shown as one example of such a solvent. Other examples of solvents or solvent mixtures having similar properties or functionality may be identified by the skilled man with the aid of the present disclosure. Ethyl acetoacetate has an acidic alpha-hydrogen which will be neutralized in the presence of a hydroxide, resulting in the formation of exothermic heat from the reaction.
  • the amount of co-solvent required in the method of the present invention will vary depending on the type of surfactant precursor which is used.
  • solid AKD may require a somewhat larger amount of co- solvent to be used than liquid AKD.
  • an amount of of 1-100 % by weight relative to the surfactant precursor will allow a sufficient amount of water to be mixed with the surfactant precursor in order to achieve rapid activation.
  • the amount of co-solvent may also be higher, for example such that the surfactant precursor may be fully dissolved in the co-solvent.
  • the surfactant precursor, alkaline compound, water and co-solvent may be either partially or fully dissolved in the mixture of step b).
  • combinations of two or more methods of providing a high contact surface area in the present invention may be employed.
  • a non-limiting example of such a combination would be a combination of a dispersion of solid particles with the addition of a suitable co- solvent as defined above.
  • the above mentioned embodiments merely represent examples of methods of providing a high contact surface area between the surfactant precursor and water. Other methods of providing a high contact surface area may be apparent to a person skilled in the art without deviating from the spirit and scope of the present invention.
  • the activation of the surfactant precursor according to the method of the invention is preferably performed under alkaline conditions.
  • the pH of the reaction mixture of the inventive method should be sufficient to cause alkaline hydrolysis of the surfactant precursor resulting in the formation of the corresponding surfactant.
  • the required pH may also depend to a certain extent on the contact surface area as discussed above. The higher the contact surface area, the lower the pH required.
  • the pH should preferably be 10 or higher in order for an acceptably high rate of activation to be attained. In some embodiments, a higher pH may be required to achieve the rapid activation. In an embodiment, the pH may be 11 or higher. In another embodiment , the pH may be 12 or higher.
  • the alkaline compound for use with the present invention should be a compound capable of producing aqueous solutions having a pH value of 10 or higher.
  • the alkaline compound should be a compound capable of producing aqueous solutions having a pH value of 11 or higher.
  • the alkaline compound should be a compound capable of producing aqueous solutions having a pH value of 12 or higher.
  • the alkaline compound may also be a solution or a dispersion of an alkaline compound in water or in a suitable organic solvent, such as for example ethanol.
  • the alkaline compound is an alkaline metal hydroxide. In another embodiment, said alkaline compound is sodium hydroxide or potassium hydroxide.
  • the alkaline compound of the invention may be added in solid form or in solution. Examples of solid form include powders, granules pellets and tablets. Examples of solutions include solutions in water or organic solvents. Generally, solutions having a concentration of 0.1-10 M of hydroxide will be suitable for use with the invention.
  • the alkaline compound may also be added in solid form and allowed to dissolve during the course of the activation reaction.
  • said alkaline compound is added in solid form.
  • the alkaline compound may also be a compound which produces heat upon dissolution in water.
  • Non limiting examples of such compounds include solid alkaline metal hydroxides, such as potassium hydroxide or sodium hydroxide.
  • said alkaline compound is solid potassium hydroxide.
  • said alkaline compound is sodium hydroxide.
  • An embodiment, wherein said alkaline compound is a compound which produces heat upon dissolution in water may be especially useful, since the extra heat generated upon dissolution of the compound further accelerates the activation reaction.
  • the addition of water speeds up the activation reaction by two different mechanisms, 1) by the intrinsic ability of water to speed up the activation rate, and 2) by allowing heat evolution through alkaline compound dissolution.
  • the amount of alkaline compound that is required may be determined by a person skilled in the art.
  • the amount of alkaline compound may also be a molar excess, i.e. more than required for the reaction.
  • a person skilled in the art can adjust the activation rate by increasing or decreasing the amount of a solid alkaline compound (for example sodium or potassium hydroxide tablets or powder, the morphology of the hydroxide will also have an effect on dissolution rate and, thus, on obtained maximum temperature of the system) or by use of a solution of the hydroxide to avoid the contribution of exothermal heat which may originate from the dissolution the solid hydroxide.
  • a solid alkaline compound for example sodium or potassium hydroxide tablets or powder, the morphology of the hydroxide will also have an effect on dissolution rate and, thus, on obtained maximum temperature of the system
  • a solution of the hydroxide to avoid the contribution of exothermal heat which may originate from the dissolution the solid hydroxide.
  • the reaction rate by controlling the cooling rate through selection of more or less insulation of the reaction beaker, or by adjusting the size of the batch, etc.
  • the reaction rate of the activation reaction is substantially increased by heat provided by an exothermic process in the reaction mixture.
  • said exothermic process comprises dissolution of a solid compound in a solvent.
  • Saponification of the ester may also probably occur to some extent, giving ethanol and acetoacetate, which, in turn will decompose to acetone by decarboxylation.
  • the use of ethyl acetoacetate may therefore be considered interesting in applications where ethanol and acetone are desired, or acceptable, by-products in the formulation, remaining after activation.
  • said exothermic process comprises an acid/base neutralization reaction.
  • Activation of surfactant precursor according to the prior art using dry ethanol/KOH carries the inherent risk of explosion or fire involved in the use of highly flammable solvents such as ethanol.
  • the present invention provides routes for rapid activation of surfactant precursor using water alone as solvent, or using solvents or solvent mixtures with a high flashpoint, such as for example dilute ethanol/water mixtures, thus eliminating or reducing the flashpoint issues inevitably connected to the ethanol based activation protocols of the prior art.
  • high flashpoint generally refers to compounds or compositions having a flashpoint above 60 °C.
  • low flashpoint generally refers to compounds or compositions having a flashpoint below 30 °C.
  • the present invention only involves high flashpoint compounds. In another embodiment, the present invention only involves non- or low-flammable compositions.
  • high flashpoint compositions may include mixtures or solutions of a low flashpoint compound with a high flashpoint compound, wherein the resulting mixture or solution has a high flashpoint.
  • thermolabile nature of the surfactant formed upon activation a surfactant precursor according to the present invention makes the temperature at which the activation reaction is performed important. If a high temperature is required for activation, the activation reaction should preferably proceed quickly in order to prevent that the formed surfactant is decomposed prematurely. Activation of the surfactant precursor according to the invention proceeds quickly at high temperatures as well as at low temperatures, which allows rapid preparation of the thermolabile surfactant without significant premature decomposition of the surfactant.
  • the inventive method for activating a surfactant precursor is advantageous in that it allows rapid activation at temperatures commonly used in industrial and domestic washing and laundry applications.
  • the activation reaction of step c) is performed at a temperature not higher than 95 0 C. In another embodiment, said temperature is not higher than 65 °C. In yet another embodiment, said temperature is not higher than 45 0 C.
  • the surfactant precursor of the present invention can be synthesized by chlorination of fatty acids followed by dimerisation of the formed fatty acid chlorides. Different fatty acids can be used, resulting in a surfactant precursor compound comprising the corresponding fatty acid residues, which then correspond to R 1 and R 2 . Hence, a wide spectrum of different surfactant precursor compounds can be obtained by use of different fatty acids and combinations thereof.
  • Fatty acids that can be used in the synthesis of a surfactant precursor according to the present invention may comprise, but are not limited to, caproic, caprylic, capric, lauric, myristic, palmitic, palmitoleic, stearic, isostearic, oleic, linoleic, linolenic, arachidic, gadoleic, behenic and erucic acids and combinations thereof.
  • the fatty acids used in the synthesis of the surfactant precursor may be derived from naturally occurring or synthetically produced fats or oils.
  • useful fats and oils are soybean oil, rapeseed oil, oiticica oil, tung oil, castor oil, tall oil, butterfat, lard, tallow, herring oil, menhaden oil, sardine oil, whale oil, olive oil, palm oil, safflower oil, sesame oil, sunflower oil, linseed oil, babassu oil, coconut oil, palm kernel oil, corn oil, cottonseed oil and groundnut oil.
  • the invention further provides a method as described above for activating a surfactant precursor as defined by the general formula I, wherein said activation results in the formation of a surfactant having the general formula Il
  • R 1 and R 2 are hydrophobic moiety, or as a precursor for a salt of said surfactant.
  • the surfactant obtained upon activation of a surfactant precursor according to the method of the present invention has been found to be susceptible to temperature controlled decomposition into CO 2 , HCO3 " or CO3 2" (depending on pH) and an oil-like (if liquid), hydrophobic residue, thereby reducing its surface activity. Furthermore, said surfactant is stable to premature and/or thermally uncontrollable degradation over a wide pH range and is thus protected from unintentional decomposition at alkaline, neutral or acidic conditions (generally at pH > pK a ). Depending on present pH conditions, a salt of the described surfactant may be active.
  • a further characteristic of a surfactant obtained upon activation of a surfactant precursor according to the method of the present invention is that its rate of decomposition, and thus its rate of inactivation, can be effectively controlled by temperature at substantially constant pH conditions. Its rate of decomposition generally increases with increasing temperature.
  • hydrophobic moiety or moieties R 1 and/or R 2 in formulas I or Il may independently be a straight-chain, branched- chain or cyclic, saturated or unsaturated, optionally substituted, aliphatic group; an optionally substituted aromatic group; an optionally substituted hydrophobic polyoxyalkylene group, such as an optionally substituted polyoxypropylene group; an optionally substituted perfluoroalkyl group; an optionally substituted polysiloxane group; a lignin or rosin derivative; or a combination thereof.
  • substituted in relation to the hydrophobic moiety or moieties, relates to the substitution of an organic group with any substituents not changing the hydrophobic nature of said moiety or the amphiphilic nature of a surfactant obtained upon activation of the compound of the invention.
  • the hydrophobic moiety or moieties is/are preferably independently selected from a straight-chain, branched-chain or cyclic, saturated or unsaturated, optionally substituted, aliphatic group; an optionally substituted aromatic group; and any combination thereof. More preferably, the hydrophobic moiety or moieties is/are independently selected from a straight- chain or branched-chain, saturated or unsaturated, optionally substituted, C 4 - C-30 alkyl, or C4-C22 alkyl.
  • any hydrophobic moieties R 1 and R 2 present in the surfactant precursor are independently selected from -(CH 2 )i 3 -CH 3 and -(CH 2 )i 5 -CH 3 .
  • the groups listed above are common, cheap, safe and well-functioning hydrophobic groups.
  • hydrophobic moieties R 1 and R 2 are present in a surfactant precursor in combinations as disclosed in Table 1.
  • hydrophobic moieties for the compounds for use as surfactant precursors in accordance with the present invention are, among others, the hydrophilic- lipophilic balance (HLB) and the Krafft temperature of the surfactant. The determination of these parameters is within the abilities of a person of skill in the art, but the two concepts are nevertheless outlined below for completeness.
  • hydrophilic-lipophilic balance (HLB) of a given surfactant is a well-known characteristic, tabulated for commercial surfactants and used extensively for selection of a suitable surfactant for a given application.
  • a high HLB number means that the surfactant in question has a high affinity for the water-phase if present in a water + oil system. If an emulsion is prepared from such a system, the result is normally an oil-in-water emulsion. On the other hand, if the HLB number is low, the surfactant has a high affinity for the oil phase, and water-in-oil emulsions are normally formed.
  • the HLB number of a surfactant is influenced by the chemical structure of both hydrophilic and hydrophobic groups of the surfactant.
  • the HLB parameter can be varied mainly through selection of hydrophobic group. As an example, those surfactants having a shorter carbon chain as hydrophobic group(s) will have a higher HLB number (will have a higher affinity for water) than those having longer carbon chains.
  • the Krafft temperature is the temperature at which the solubility in water increases very dramatically.
  • a surfactant provided by a surfactant precursor according to the invention it is important to consider the Krafft temperature of the surfactant, so as to assure dissolution of the surfactant at the temperature in question.
  • a well-known way of decreasing the Krafft temperature of a surfactant is the use of one or several double bonds in the hydrophobic group(s), creating a bent carbon chain which in turn renders packing conditions in the solid state less favourable.
  • those surfactant precursors in the above listing comprising at least one double bond should provide surfactants having a lower Krafft temperature than the corresponding compounds without the double bond.
  • Another well- known way of lowering the Krafft temperature of a surfactant is to introduce branching in the hydrophobic group.
  • a compound obtained upon activation of a surfactant precursor of the present invention acts as an anionic surfactant (i.e. in its salt form) at pH > pK a .
  • the pK a of compounds of the present invention may vary widely, e.g. as a result of the choice of hydrophobic moieties.
  • suitable temperatures e.g. in the range from 0 to 100 0 C for employing a compound obtained upon activation of a surfactant precursor of the present invention.
  • the surfactant obtained upon activation of a surfactant precursor of the present invention may be a dispersing agent.
  • the rapid activation achieved by the method of the invention further enables the use of the surfactant precursor and a surfactant obtained thereby in a number of important industrial and domestic applications.
  • HLB hydrophilic/lipophilic balance
  • the rapid activation achieved by the method of the invention allows a first time-resolved HLB shift to be created upon activation of the surfactant precursor to a surfactant having a certain HLB value in the presence of another surfactant having a substantially different HLB value.
  • a second time-resolved HLB shift may be created upon decomposition of the surfactant having a certain HLB value in the presence of another surfactant having a substantially different HLB value.
  • the present invention provides a method of providing a time-resolved shift in an aggregate hydrophilic/lipophilic balance in a liquid medium, by activation of a surfactant precursor according to the method of the present invention to a first surfactant having a certain hydrophilic/lipophilic balance, in the presence of a second surfactant having a hydrophilic/lipophilic balance which is substantially different from that of said first surfactant.
  • the surfactant formed upon activation in step is thermolabile
  • the method further comprises the step of setting the temperature of said mixture, so as to achieve a desired decomposition rate of the thermolabile surfactant.
  • the present invention provides a method of providing a time-resolved shift in an aggregate hydrophilic/lipophilic balance in a liquid medium, comprising the steps of: a) activating a surfactant precursor according to the method of the invention to obtain a thermolabile surfactant having a certain hydrophilic/lipophilic balance, b) mixing said thermolabile surfactant with a stable surfactant having a hydrophilic/lipophilic balance which is substantially different from that of the labile surfactant, c) setting the temperature of said mixture, so as to achieve a desired decomposition rate of the thermolabile surfactant.
  • a laundry detergent comprising a surfactant obtained by activation of a surfactant precursor in accordance with the present invention i.e. a thermolabile (soap-like) first surfactant, having a certain HLB value, in addition to a, preferably stable, second surfactant, having an HLB value which is substantially different from the HLB value of the thermolabile surfactant, may display an enhanced stain removal efficiency due to the fact that the hydrophilic/lipophilic balance (HLB) will change during the wash cycle as the thermolabile surfactant breaks down.
  • HLB hydrophilic/lipophilic balance
  • compositions of this formulation may be selected by the skilled person to provide alternative compositions, taking into account the functional significance of each component.
  • the period of time over which an HLB shift is effected may be controlled by selection of suitable process parameters, e.g. in terms of reaction temperature and pH.
  • the present invention provides a surfactant precursor composition for preparing a thermolabile surfactant, said composition comprising: i) a surfactant precursor as defined above, ii) an organic polar solvent in which both said surfactant precursor and water are at least partially soluble.
  • R 1 and R 2 of the surfactant precursor in this aspect of the invention may be as defined above for the method of the first aspect of the invention.
  • Such a composition is advantageous in that it may be stored for a prolonged period of time without significant degradation, and then be combined with a composition comprising water and an alkaline compound to achieve activation of the surfactant precursor to the corresponding surfactant.
  • Non-limiting examples of polar organic co-solvents useful with the invention include methanol, ethanol, isopropanol, dipropylene glycol methyl ether, propylene glycol n-butyl ether, ethyl acetoacetate and mixtures thereof.
  • the polar organic co-solvent is ethanol.
  • the polar organic co-solvent is ethyl acetoacetate.
  • said surfactant precursor composition may further comprise water at a concentration of 0.5-50 % by weight of the total composition.
  • the surfactant precursor provided in the form of a nanoemulsion can be stored at room temperature without significant decomposition. Such a nanoemulsion may advantageously be employed in a method of activating a surfactant precursor according to the present invention.
  • Another aspect of the invention relates to the use as a surfactant precursor composition of a nanoemulsion in water of a surfactant precursor as defined above.
  • R 1 and R 2 of the surfactant precursor in this aspect of the invention may be as defined above for the method of the first aspect of the invention.
  • the nanoemulsion in water may preferably further comprise a surfactant for stabilizing said nanoemulsion.
  • a surfactant for stabilizing a nanoemulsion may be readily identified by a person skilled in the art.
  • a non-limiting example of a suitable surfactant for stabilizing said nanoemulsion is Berol OX 91-8.
  • the invention provides a surfactant precursor kit, comprising: i) a surfactant precursor composition comprising a surfactant precursor as defined above, ii) an activator composition, comprising an alkaline compound as defined above.
  • the surfactant precursor composition of such a surfactant precursor kit comprises a nanoemulsion of said surfactant precursor in water.
  • the surfactant precursor composition of such a surfactant precursor kit comprises a polar organic co- solvent.
  • said activator composition comprises a solid alkaline compound.
  • said activator composition comprises an aqueous solution of an alkaline compound.
  • the surfactant precursor composition may for example comprise a nanoemulsion of said surfactant precursor in water and said activator composition may comprise an aqueous KOH solution.
  • surfactant precursor kit said surfactant precursor composition and/or said activator composition may further comprise a polar organic co-solvent.
  • the method of the present invention may also be used in the preparation of a dispersion comprising solid particles, liquid droplets or gas bubbles dispersed, as an internal phase, in a fluid, as an external phase, by means of a surfactant, as a dispersing agent, wherein said surfactant is obtained by activation of a surfactant precursor according to a method as defined above.
  • a surfactant as a dispersing agent
  • the rapid activation achieved by the method of the invention enables the use of the surfactant precursor and a surfactant obtained thereby in a number of important industrial and domestic applications, for example common automatic laundry or washing procedures, that are restrained to certain process parameters in terms of time, temperature and pH.
  • Said surfactant may be active in any kind of dispersion, the preparation of which can be accomplished according to procedures well known to the skilled man (such as agitation, shearing or spraying).
  • a dispersion may be an aerosol, a colloid, an emulsion, a foam, a gel, a sol or a suspension.
  • the external phase of such a dispersion may be an aqueous phase as well as an oil phase or air.
  • the skilled man is able to routinely examine the decomposition rate, as manifested by delayed dispersion breaking and/or the breaking rate at different temperatures in such a dispersion or as manifested by for example a decrease in foamability.
  • the skilled man is able to choose suitable temperatures (e.g. in the range from 0 to 100 0 C) for employing the dispersion.
  • suitable temperatures e.g. in the range from 0 to 100 0 C
  • the rate of decomposition can be effectively controlled by temperature at substantially constant pH conditions.
  • the rate of decomposition generally increases with increasing temperature.
  • a method for preparing a dispersion comprising solid particles, liquid droplets or gas bubbles dispersed, as an internal phase, in a fluid, as an external phase, by means of a surfactant, as a dispersing agent, said method comprising the steps of a) providing a surfactant precursor as defined above, b) activating said surfactant precursor to a surfactant according to the inventive method described above, c) dispersing a mixture of said internal phase, said external phase and said surfactant.
  • a method for preparing a dispersion comprising solid particles, liquid droplets or gas bubbles dispersed, as an internal phase, in a fluid, as an external phase, by means of a surfactant as a dispersing agent, said method comprising the steps of a) providing a mixture of said internal phase, said external phase and a surfactant precursor as defined above, b) activating said surfactant precursor to a surfactant according to the inventive method described above, c) dispersing said mixture.
  • the objects of the present invention are accomplished by a method for breaking a dispersion comprising solid particles, liquid droplets or gas bubbles dispersed, as an internal phase, in a fluid, as an external phase, by means of a surfactant as a dispersing agent, said method comprising the steps of a) providing a surfactant precursor as defined above, b) activating said surfactant precursor to a surfactant according to the inventive method described above, c) dispersing a mixture of said internal phase, said external phase and said surfactant, d) providing said dispersion at a temperature where it is substantially stable, and e) setting the temperature of said dispersion, so as to achieve a desired decomposition rate of the surfactant.
  • the objects of the present invention are accomplished by a method for breaking a dispersion comprising solid particles, liquid droplets or gas bubbles dispersed, as an internal phase, in a fluid, as an external phase, by means of a surfactant as a dispersing agent, said method comprising the steps of a) providing a mixture of said internal phase, said external phase and a surfactant precursor as defined above, b) activating said surfactant precursor to a surfactant according to the inventive method described above, c) dispersing said mixture, d) providing said dispersion at a temperature where it is substantially stable, and e) setting the temperature of said dispersion, so as to achieve a desired decomposition rate of the surfactant.
  • step a) allows for the surface activity in a composition comprising the surfactant precursor to be rapidly switched on at a desirable occasion, thereby changing the properties of the composition.
  • the surfactant precursor in step a) is provided in the form of a nanoemulsion of the surfactant precursor in water. In another embodiment, the surfactant precursor in step a) is provided in the form of a mixture with a suitable co-solvent as described above.
  • the surfactant obtained upon activation of a surfactant precursor of the invention is susceptible to an increased rate of decomposition and inactivation by increasing temperature. This property allows for controlled breaking of a dispersion at a desirable moment and/or at a desirable rate. Hence, in any suitable application, the properties of an initially dispersed composition may be changed as desirable.
  • the skilled man is able to routinely examine the required temperature for a desired decomposition rate.
  • the temperature is dependent on the surfactant, the external phase and the internal phase components, as well as on pH (see above).
  • the dispersion is preferably provided at a temperature in the range from about 0 to about 40 0 C, preferably from about 10 to about 30 0 C, at which the dispersion is virtually stable (i.e. stable for e.g. hours or days).
  • the dispersion may also be provided at a higher temperature, such as in the range from about 40 to about 95 °C. This is possible, since the activation of the surfactant precursor according to the method of the present invention proceeds very quickly.
  • the temperature By raising the temperature to a range from about 40 to about 100 0 C, preferably from about 60 to about 95 0 C, the dispersion is broken faster due to increased rate of decomposition and deactivation of the surfactant (i.e. decomposition within e.g. minutes or hours).
  • the rate of decomposition as manifested by delayed dispersion breaking and/or the breaking rate, can thus be effectively controlled by temperature at substantially constant pH conditions.
  • the rate of decomposition generally increases with increasing temperature.
  • the objects of the present invention are attained by the provision of a method for reducing the surface tension between a liquid and another phase, comprising adding to said liquid a surfactant precursor as defined above, and activating said surfactant precursor to a surfactant according to the method of the present invention.
  • a surfactant precursor as defined above
  • activating said surfactant precursor to a surfactant according to the method of the present invention.
  • Particular variants and options for the surfactant precursor used in the inventive method for reducing surface tension are as discussed above.
  • Results are shown in Table 2, and it is obvious that significant activation (> 50 % of the AKD activated within 2 minutes) can be obtained by this route, giving a useful surfactant concentrate containing only low amounts of solvent (exemplified here with isopropanol).
  • Emulsions of AKD in 0.5 M KOH solutions were prepared by the following well known mechanical and surface chemical methods, in order to obtain a wide range of particle sizes (measured by a MasterSizer instrument, produced by Malvern Instruments):
  • Magnetic stirring 3.0 g of AKD (Precise 900) was added to a 100 ml volumetric flask together with a 2 cm magnetic stirring rod. The AKD was then emulsified in a 0.5 M aqueous solution of KOH, using first manual shaking (about 10 seconds), followed by magnetic stirring at 1000 rpm speed for the remainder of the experiment.
  • AKD Precise 900
  • High shear emulsification An Ultrathurrax mixer, set at 10000 rpm speed, was used to homogenize a mixture of AKD and ethanol, prepared just as the one in the magnetic stirring protocol above. The high shear mixing was applied in 2 minute periods spaced apart by 15 minute intervals.
  • Phase inversion emulsification 3.0 g of Precise 900 and 3.0 g of Berol OX 91-8 were mixed and 22 ml KOH (0.5 M) in water was added at a rate of 2 ml/min. A 3 cm magnet with 500 rpm stirring speed was used during the addition of water to the AKD/surfactant mixture.
  • AKD- in-water emulsions preferably consisting of very small AKD particles to speed up the activation, were prepared by the inversion emulsification protocol of Example 4, with the KOH solution being replaced by distilled water and the amount of water reduced to 5.5 ml (the emulsification aborted just after the phase inversion, which was identified by the onset of decrease of viscosity of the emulsion; up to the phase inversion the viscosity increased constantly).

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Abstract

La présente invention porte sur un procédé pour une activation rapide d'un précurseur d'agent tensio-actif, ayant la formule générale (I), dans laquelle au moins l'un parmi R1 et R2 est une fraction hydrophobe, conduisant à la formation d'un agent tensio-actif, caractérisé par le fait que ladite activation est effectuée par les opérations consistant à : a) se procurer ledit précurseur d'agent tensio-actif, b) mélanger le précurseur d'agent tensio-actif avec de l'eau et un composé alcalin pour fournir une aire de contact de surface élevée entre ledit précurseur d'agent tensio-actif et l'eau et le composé alcalin, de telle sorte que le pH du mélange résultant soit de 10 ou plus, c) amener le précurseur d'agent tensio-actif à réagir avec ladite eau et un composé alcalin.
PCT/EP2008/010536 2007-12-12 2008-12-11 Activation rapide d'un précurseur d'agent tensio-actif Ceased WO2009074321A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9700915B2 (en) 2010-12-17 2017-07-11 Cellutech Ab Method for production of superhydrophobic surfaces

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4861376A (en) * 1988-11-10 1989-08-29 Hercules Incorporated High-solids alkyl ketene dimer dispersion
US20060009571A1 (en) * 2002-10-18 2006-01-12 Basf Aktiengesellschaft Aqueous polymer dispersions containing alkyldiketenes, methods for the production thereof, and their use
EP1783201A1 (fr) * 2005-11-04 2007-05-09 YKI, Ytkemiska Institutet AB Précurseur de tensioactif

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4861376A (en) * 1988-11-10 1989-08-29 Hercules Incorporated High-solids alkyl ketene dimer dispersion
US20060009571A1 (en) * 2002-10-18 2006-01-12 Basf Aktiengesellschaft Aqueous polymer dispersions containing alkyldiketenes, methods for the production thereof, and their use
EP1783201A1 (fr) * 2005-11-04 2007-05-09 YKI, Ytkemiska Institutet AB Précurseur de tensioactif

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9700915B2 (en) 2010-12-17 2017-07-11 Cellutech Ab Method for production of superhydrophobic surfaces

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