EP1109883B2 - Verfahren zur effizienzsteigerung von tensiden und verfahren zur unterdrückung lamellarer mesophasen in mikroemulsionen sowie ein tensid, welchem ein additiv beigefügt ist - Google Patents

Verfahren zur effizienzsteigerung von tensiden und verfahren zur unterdrückung lamellarer mesophasen in mikroemulsionen sowie ein tensid, welchem ein additiv beigefügt ist Download PDF

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Publication number
EP1109883B2
EP1109883B2 EP99953661.8A EP99953661A EP1109883B2 EP 1109883 B2 EP1109883 B2 EP 1109883B2 EP 99953661 A EP99953661 A EP 99953661A EP 1109883 B2 EP1109883 B2 EP 1109883B2
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European Patent Office
Prior art keywords
block
water
surfactants
oil
surfactant
Prior art date
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Expired - Lifetime
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EP99953661.8A
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German (de)
English (en)
French (fr)
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EP1109883B1 (de
EP1109883A2 (de
Inventor
Jürgen Allgaier
Lutz Willner
Dieter Richter
Britta Jakobs
Thomas Sottmann
Reinhard Strey
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Forschungszentrum Juelich GmbH
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Forschungszentrum Juelich GmbH
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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
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C11D17/0021—Aqueous microemulsions
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • 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
    • C11D3/37—Polymers

Definitions

  • the invention relates to a process for increasing the efficiency of surfactants with simultaneous suppression of lamellar mesophases, in particular in microemulsions and emulsions, as well as surfactants, to which an additive is admixed.
  • Emulsions and microemulsions are stabilized in the prior art by nonionic, anionic or cationic surfactants.
  • the surfactants are able to solubilize a non-polar solvent (oil) in a polar solvent (eg water) or water in oil.
  • the efficiency of the surfactants is expressed in the amount of surfactant needed to solubilize a certain amount of oil in the water or vice versa.
  • water-oil-surfactant mixtures a distinction is additionally made between emulsions and microemulsions. While microemulsions are thermodynamically stable, emulsions are thermodynamically unstable and disintegrate.
  • Lamellar mesophases can occur in microemulsion systems. Lamellar mesophases lead to optical anisotropy and increased viscosity. These properties are undesirable for detergents, for example, since the lamellar mesophases are not washable.
  • additives generally affect the temperature behavior of the emulsions and microemulsions.
  • the phase diagram shows a shift of the single-phase areas for oil-water-surfactant mixtures into other temperature ranges when an additive is added.
  • the displacements can be on the order of 10 ° C.
  • detergent formulations must be changed in order to adapt to the newly adjusting temperature behavior of the single-phase region.
  • the European patent EP 0 018 085 B1 discloses an explosive having good blasting properties in the form of a water - in - oil microemulsion.
  • the microemulsion contains a block copolymer.
  • the font DE 196 34 477 A1 discloses the preparation of a microemulsion containing AB block copolymers with a nonpolar solvent-soluble block A and a polar solvent-soluble block B.
  • the U.S. Patent 5,162,378 discloses microemulsions containing cetyl dimethicone copolyol and, in some examples, the methoxy PEG-22 / dodecyl copolymer (Elfacos E200).
  • the object of the invention to increase the efficiency of surfactants. Furthermore, the occurrence of lamellar phases in microemulsions or water, oil, surfactant mixtures should be suppressed.
  • the temperature behavior of the emulsions and microemulsions should remain unaffected by the addition of the additive, that is, the position of the single-phase region in the phase diagram should not be substantially influenced by the addition of the additives with respect to the temperature.
  • An additive is to be created which does not influence the position of the single-phase region with respect to the temperature. It is also intended to provide an additive which has the above-mentioned advantages and e.g. a detergent can be added without a change in the formulation of the remaining detergent formulation must be made. It is a possibility to create microemulsions whose size of the emulsified liquid particles correspond to those of emulsions.
  • an AB block copolymer with a water-soluble block A and a water-insoluble block B is added as an additive, wherein as block A of the AB block copolymer, a polyethylene oxide (PEO) is used and as block B of the AB block copolymer a polydiene or an at least partially hydrogenated polydiene is used and solved by the preamble of claim 2 characterized in that the water-oil surfactant mixture as an additive, an AB block copolymer having a water-soluble block A and a water-insoluble block B added is, wherein the blocks A and B have a molecular weight between 500-5000 g / mol.
  • PEO polyethylene oxide
  • the object is achieved in that an oil-water surfactant mixture in microemulsions as an additive is added an AB block copolymer having a water-soluble block A and a water-insoluble block B, wherein the blocks A and B has a molecular weight between 500-5000 g / mol.
  • the addition of the AB block copolymer to the water-oil-surfactant mixture does not change the position of the single-phase region in the phase diagram in the temperature region, the efficiency of the surfactant mixture is considerably increased, lamellar mesophases are suppressed in microemulsions.
  • microemulsions retain their characteristic properties while increasing their structure size;
  • the emulsified structures take on sizes of up to about 2000 angstroms.
  • a microemulsion is obtained which has the structure sizes of an emulsion but is thermodynamically stable.
  • the size of the emulsified liquid particles depends on the temperature and the amount of block copolymer added, or thus on the composition of the surfactant mixture.
  • the blocks A and B can assume molecular weights between 500 and 60,000 u.
  • a polyethylene oxide (PEO) block is preferably used.
  • all blocks A that are water-soluble may be used so that they form an amphiphile in conjunction with block B.
  • block A can be exemplified by polyacrylic acid, polymethacrylic acid, polystyrenesulfonic acid and their alkali metal salts in which at least partial substitution of the acid function by alkali metal cations, polyvinylpyridine and polyvinyl alcohol, polymethylvinylether, polyvinylpyrrolidine, polysaccharides and mixtures thereof are mentioned.
  • block B various water-insoluble components of said molecular weight are used.
  • block B may be the product of anionic 1,2-, 3,4-, or 1,4-polymerization of dienes.
  • block B may still be the product of at least partial hydrogenation of the polydienes.
  • Typical monomeric constituents are 1,3-butadiene, isoprene, all constants of dimethylbutadiene, 1,3-pentadiene, 2,4-hexadienes, ⁇ -methylstyrene, isobutylene, ethylene, propylene, styrene or alkyl acrylates and alkyl methacrylates where the alkyl group contains between 2 and 20 carbon atoms for use.
  • Block B may also be polydimethylsiloxane.
  • Block B the polymer of a single monomer or a mixture of monomers can be used.
  • Block B may have as side chains methyl, ethyl, vinyl-phenyl or benzyl groups.
  • the double bonds in the polydiene chain as well as in the vinyl groups, which may exist as a side chain, may be either fully or partially hydrogenated.
  • any sufficiently amphiphilic block copolymer can be used.
  • the AB block copolymers used according to the invention can preferably be obtained from an anionic polymerization.
  • At lower molecular weights of blocks A and B in the order of about 500-5000 g / mol for blocks A and B, particularly advantageous properties of the AB block copolymers according to the invention in application products are observed.
  • the polymers with these low molecular weights dissolve quickly and well. This applies, for example, to solutions in soaps and detergents.
  • Block A should be as polar as possible and block B preferably nonpolar. This increases the amphiphilic behavior.
  • Block A should be water-soluble and block B should be soluble in non-polar media.
  • block B is soluble in mineral oils or aliphatic hydrocarbons or in mineral oils and aliphatic hydrocarbons. This also applies at room temperature.
  • AB block copolymers of the type ABA and BAB which are referred to as triblock copolymers.
  • PX / Y additive having a molecular weight in 1000 g / mol X of hydrophobic alkyl chain (hydrogenated 1,4-polyisoprene) and a molecular weight in 1000 g / mol Y of polyethylene oxide.
  • P22 / 15 the alkyl chain has a molecular weight of 22,000 g / mol and the polyethylene oxide chain has a Molecular weight of 15000 g / mol.
  • the additives shown in this way are AB block copolymers.
  • the compounds shown here by way of example can be obtained by the production process from the DE 196 34 477 A1 to be obtained.
  • FIG. 1 represents the type of phase diagram of the prior art, which is the basis for the FIGS. 1 to 8 supplies.
  • the temperature T is plotted against the total surfactant concentration ⁇ for the system water / n-tetradecane-C 6 E 2 and a water / n-tetradecane ratio of 1: 1.
  • the Einphasen is the Einphasen which 1 of the mixture.
  • This area is followed by a closed three-phase area 3 in the direction of lower surfactant concentrations.
  • Above and below the phase boundary lines are two-phase regions 2.
  • the point at which all phase regions meet is determined by the surfactant concentration and the temperature Are defined. The more shifted to small values, the larger the structure size of the microemulsions.
  • FIGS. 2 to 9 T / ⁇ diagrams refer to systems having a constant water / oil volume ratio of 1: 1 and will be discussed in general terms below.
  • curves are plotted, each with a ⁇ value, which characterizes the limitation of the respective single-phase region belonging to a ⁇ value.
  • the apex of the respective curve is the point at which different polyphase regions meet.
  • the further the peak of a curve is located at lower surfactant concentrations, ie ⁇ values, the greater the efficiency of the surfactant C by the addition of the block copolymer D.
  • FIG. 2 shows how the efficiency of the total surfactant increases with the addition of the block copolymer.
  • no lamellar mesophases occur in the mixtures investigated.
  • the efficiency of the total surfactant is also reflected in the FIG. 4 shown example increased and the temperature position is maintained substantially. Lamellar phases are not observed.
  • FIG. 6 is the same behavior to watch as in FIG. 5 .
  • FIG. 7 and 8th is also a significant increase in efficiency observed.
  • the gray dots are PI5 / PEO15 and the triangles are P5 / 15.
  • FIG. 9 the efficiency increase in an anionic surfactant system (water + NaCl) / n-decane-AOT-P5 / 5 is shown.
  • FIG. 9 the efficiency increase in an anionic surfactant system (water + NaCl) / n-decane-AOT-P5 / 5 is shown.
  • phase behavior is not determined by the temperature but by the addition of a cosurfactant (octanol).
  • octanol cosurfactant
  • FIG. 11 documents in an overview the invention very strong increase in efficiency of the block copolymer admixtures. Plotted are the total surfactant concentrations at the crossing point as a function of the addition ⁇ of the block copolymer. In contrast to conventional surfactant mixtures, a very small addition of ⁇ leads to a greater decrease in the block copolymers , and therefore to greater efficiency.
  • the value of the water / oil interfacial tension minimum correlates with the efficiency of the surfactant mixture, e.g. for the washing process the lowest possible interfacial tension is desired.
  • the occurrence of lamellar mesophases is suppressed.
  • the temperature behavior of the microemulsions remains unchanged, that is, the position of the single-phase region with respect to the temperature in the phase diagram is not influenced by the addition of the additives used according to the invention. Therefore, the formulation of a detergent must not be changed to cause a constant position of the single-phase region with respect to the temperature in the single-phase diagram.
  • the AB block copolymers according to the invention can not only be used in detergents; they can be used with the same effect, for example, as additives in food and cosmetics and in all industrial or technical applications of microemulsions and emulsions, for example in petroleum production, in soil remediation and in the application as eg reaction medium.
  • the microemulsions prepared by means of the addition according to the invention of the AB block copolymers have emulsified liquid volumes whose size corresponds to those of emulsions.
  • the effects of the present invention can be achieved by any common use of a surfactant with the AB block copolymer in a system to be emulsified.
  • a surfactant to which an AB block copolymer according to the invention is added, and any system emulsified therewith and additionally comprising water and / or oil, are therefore encompassed by the invention.
  • the effects of the invention are not limited to emulsions and microemulsions, but affect the behavior of surfactants in general in the manner described.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Colloid Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • General Preparation And Processing Of Foods (AREA)
EP99953661.8A 1998-08-28 1999-08-26 Verfahren zur effizienzsteigerung von tensiden und verfahren zur unterdrückung lamellarer mesophasen in mikroemulsionen sowie ein tensid, welchem ein additiv beigefügt ist Expired - Lifetime EP1109883B2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19839054A DE19839054A1 (de) 1998-08-28 1998-08-28 Verfahren zur Effizienzsteigerung von Tensiden bei simultaner Unterdrückung lamellarer Mesophasen sowie Tenside, welchen ein Additiv beigefügt ist
DE19839054 1998-08-28
PCT/DE1999/002748 WO2000012660A2 (de) 1998-08-28 1999-08-26 Verfahren zur effizienzsteigerung von tensiden bei simultaner unterdrückung lamellarer mesophasen sowie tenside, welchen ein additiv beigefügt ist

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Publication Number Publication Date
EP1109883A2 EP1109883A2 (de) 2001-06-27
EP1109883B1 EP1109883B1 (de) 2004-10-27
EP1109883B2 true EP1109883B2 (de) 2014-09-03

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EP99953661.8A Expired - Lifetime EP1109883B2 (de) 1998-08-28 1999-08-26 Verfahren zur effizienzsteigerung von tensiden und verfahren zur unterdrückung lamellarer mesophasen in mikroemulsionen sowie ein tensid, welchem ein additiv beigefügt ist

Country Status (6)

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US (2) US6677293B1 (ja)
EP (1) EP1109883B2 (ja)
JP (1) JP4703852B2 (ja)
AT (1) ATE280821T1 (ja)
DE (2) DE19839054A1 (ja)
WO (1) WO2000012660A2 (ja)

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EP2045320B1 (de) 2007-09-19 2012-04-25 Bubbles & Beyond Gmbh Reinigungsmittel zur Entfernung von Farbschichten von Oberflächen, Verfahren zur Herstellung des Mittels und Verfahren zur Reinigung
DE102007058342A1 (de) 2007-12-03 2009-06-04 Henkel Ag & Co. Kgaa Verminderung der Biofilmbildung durch multifunktionelle Copolymere
DE102007058343A1 (de) 2007-12-03 2009-06-04 Henkel Ag & Co. Kgaa Verminderung der Adhäsion von Schmutz, Staub und biologischem Material durch Polyesteramide
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ATE280821T1 (de) 2004-11-15
WO2000012660A3 (de) 2000-06-22
US20040054064A1 (en) 2004-03-18
EP1109883B1 (de) 2004-10-27
US7468349B2 (en) 2008-12-23
US6677293B1 (en) 2004-01-13
WO2000012660A2 (de) 2000-03-09
DE59910950D1 (de) 2004-12-02
EP1109883A2 (de) 2001-06-27

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