EP1109883B1 - Procede d'augmentation de l'efficacite de tensioactifs et de suppression simultanee de mesophases smectiques, ainsi que tensioactifs auxquels a ete ajoute un additif - Google Patents

Procede d'augmentation de l'efficacite de tensioactifs et de suppression simultanee de mesophases smectiques, ainsi que tensioactifs auxquels a ete ajoute un additif Download PDF

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Publication number
EP1109883B1
EP1109883B1 EP99953661A EP99953661A EP1109883B1 EP 1109883 B1 EP1109883 B1 EP 1109883B1 EP 99953661 A EP99953661 A EP 99953661A EP 99953661 A EP99953661 A EP 99953661A EP 1109883 B1 EP1109883 B1 EP 1109883B1
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Prior art keywords
block
water
oil
surfactants
additive
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EP99953661A
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German (de)
English (en)
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EP1109883A2 (fr
EP1109883B2 (fr
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 method for increasing efficiency of surfactants with simultaneous suppression of lamellar Mesophases especially in microemulsions and Emulsions, as well as surfactants, to which an additive is added is.
  • emulsions and microemulsions are stabilized by nonionic, anionic or cationic surfactants.
  • the surfactants can solubilize a non-polar solvent (oil) in a polar solvent (eg water) or water in oil.
  • the effectiveness of the surfactants is expressed in the amount of surfactant required to solubilize a certain proportion of oil in water or vice versa.
  • water-oil-surfactant mixtures 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 e.g. B. undesirable for detergents, since the lamellar mesophases are not washable.
  • additives generally influence the temperature behavior of the emulsions and microemulsions. A shift in the single-phase areas for oil-water-surfactant mixtures to other temperature ranges can be observed in the phase diagram when an additive is added. The shifts can be on the order of 10 ° C. However, this has the consequence that, for. B. detergent formulations have to be changed to adapt them to the new temperature behavior of the single-phase area.
  • British patent 1 103 201 discloses organosiloxaneoxyalkylene Block copolymers used as organic surface active compounds can be used.
  • British patent application 2 223 235 A discloses a composition comprising ethylene oxide - Propylene oxide block copolymer.
  • the efficiency of surfactants and increase the interfacial tension between water and oil in the presence of surfactants decrease more. Furthermore, the occurrence of lamellar phases in microemulsions or water, oil, Surfactant mixtures can be suppressed.
  • the temperature behavior of the emulsions and microemulsions is said to Addition of the additive remains unaffected, that is, the location of the single-phase area in the phase diagram by adding the additives with respect to the temperature in the are not significantly influenced. It is said to be an additive be created, which is the location of the single-phase area not affected by temperature. It an additive should also be made available, which has the advantages mentioned above and e.g. can be mixed into a detergent without a Changing the formulation of the remaining detergent formulation must be made. An opportunity is to be created to produce microemulsions, the Size of the emulsified liquid particles that of Emulsions.
  • the addition of the AB block copolymer the location of the water-oil-surfactant mixture of the single-phase area in the phase diagram in the temperature area did not change the efficiency of the surfactant mixture is significantly increased, lamellar mesophases are suppressed in microemulsions and the interfacial tension between water and oil is lowered more than by the surfactants alone. Also keep Microemulsions have their characteristic properties while increasing their structure size; so the emulsified structures take sizes of up to approx. 2000 angstroms. A microemulsion is thus obtained which has the structure sizes of an emulsion, but is thermodynamically stable. The size of the emulsified Liquid particles depend on the temperature and the added Amount of block copolymer, or therefore of the composition of the surfactant mixture.
  • Blocks A and B can assume molecular weights between 500 u and 60,000 u.
  • a polyethylene oxide (PEO) block is preferably used as block A.
  • all blocks A which are water-soluble can be used, so that they form an amphiphile in conjunction with block B.
  • block A polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid and their alkali metal salts in which the acid function has been at least partially replaced by alkali metal cations, polyvinylpyridine and polyvinyl alcohol, polymethylvinyl ether, polyvinylpyrrolidine, polysaccharides and mixtures thereof can also be mentioned as examples.
  • Various water-insoluble components of the stated molecular weight are used for block B.
  • Block B can be the product of an anionic 1,2-, 3,4-polymerization or 1,4-polymerization of dienes.
  • block B can furthermore be the product of an at least partial hydrogenation of the polydienes.
  • Typical monomeric components are 1,3 butadiene, isoprene, all constitutents of dimethylbutadiene, 1.3 pentadiene, 2.4 hexadienes, ⁇ methylstyrene, isobutylene, ethylene, propylene, styrene or alkyl acrylates and alkyl methacrylates, the alkyl group containing between 2 and 20 carbon atoms for use.
  • Block B can also be polydimethylsiloxane.
  • the polymer of a single monomer or a monomer mixture can be used as block B.
  • Block B can have methyl, ethyl, vinyl-phenyl or benzyl groups as side chains.
  • the double bonds in the polydiene chain as well as in the vinyl groups, which can exist as a side chain, can be either completely or partially hydrogenated.
  • any sufficiently amphiphilic block copolymer can be used in the present invention.
  • the AB block copolymers used according to the invention can preferably be obtained from an anionic polymerization. With 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 are observed in application products. 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 as non-polar as possible. This increases the amphiphilic behavior.
  • Block A should be water-soluble and Block B should be soluble in non-polar media.
  • Block B is advantageously 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 ABA and BAB type which are referred to as triblock copolymers, can also be used.
  • PX / Y additive with a molecular weight in 1000g / mol X of a hydrophobic alkyl chain (hydrogenated 1,4-polyisoprene) and a molecular weight in 1000g / mol Y of polyethylene oxide.
  • P22 / 15 the alkyl chain has a molecular weight of 22000 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 DE 196 34 477 A1.
  • the H 2 O / n-dean ratios realized in FIGS. 1 to 9 and 11 to 13 are 1: 1.
  • FIG. 1 shows the type of phase diagram according to the prior art, which provides the basis for FIGS. 1 to 8.
  • the temperature T is plotted against the total surfactant concentration ⁇ for the water / n-tetradecane-C 6 E 2 system and a water / n-tetradecane ratio of 1: 1.
  • the single phase area 1 of the mixture is located. This area is followed by a closed three-phase area 3 in the direction of lower surfactant concentrations.
  • T / ⁇ diagrams shown in Figures 2 to 9 refer to systems with a constant water / oil volume ratio of 1: 1 and are general below are explained.
  • Figure 2 shows how the efficiency of the total surfactant enlarged with the addition of the block copolymer. additionally is not a significant shift in the single phase area recorded on the temperature axis. This is synonymous with the fact that the block copolymer D Location of the effectiveness of the surfactant C with regard to its application temperature leaves essentially invariant. Furthermore no lamellar arises occur in the investigated mixtures Mesophases.
  • FIGS. 7 and 8 A significant increase in efficiency can also be observed in FIGS. 7 and 8. Furthermore, no lamellar phases occur in the experiments shown in FIGS. 7 and 8. In Figure 7, the gray dots are PI5 / PEO15 and the triangles P5 / 15. While the increase in efficiency of the nonionic surfactant C 10 E 4 was documented by the addition of block copolymers in FIGS. 2-8, the increase in efficiency in an anionic surfactant system (water + NaCl) / n-decane-AOT-P5 / 5 is shown in FIG.
  • Figure 11 documents an overview of the very strong increase in efficiency of the block copolymer admixtures according to the invention.
  • the total surfactant concentrations at the crossing point are shown as a function of the addition ⁇ of the block copolymer.
  • a very small addition ⁇ leads to a greater decrease in the block copolymers , and thus a strong increase in efficiency.
  • interfacial tension is shown as a function of temperature for the water / n-dean-C 10 E 4 -P5 / 5 system.
  • the interfacial tension of surfactants such as, for example, anionic, cationic and nonionic surfactants, sugar surfactants or technical surfactant mixtures, is reduced.
  • the occurrence of lamellar mesophases is suppressed.
  • the temperature behavior of the microemulsions remains unchanged, that is to say 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 does not have to be changed in order to bring about a constant position of the single-phase area 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 also be used with the same effect, for example as additives in foods and cosmetics and in all industrial or technical applications of microemulsions and emulsions, for example when used in oil production, in soil remediation and when used as a reaction medium.
  • the microemulsions produced by adding the AB block copolymers according to the invention have emulsified liquid volumes whose size corresponds to that of emulsions.
  • the effects according to the invention can be achieved by any use of a surfactant together 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, comprising additionally water and / or oil, are therefore encompassed by the invention.
  • the effects according to the invention are not limited to emulsions and microemulsions, but generally influence the behavior of surfactants in the manner described.

Claims (20)

  1. Procédé d'augmentation de l'efficacité de tensioactifs dans une émulsion ou une microémulsion d'eau et d'huile par l'ajout d'additifs ayant une partie hydrosoluble et une partie non hydrosoluble, caractérisé en ce que l'additif ajouté est un copolymère séquencé AB avec une séquence A hydrosoluble et une séquence B non hydrosoluble.
  2. Procédé pour éviter les phases lamellaires dans les mélanges eau/huile/tensioactif en microémulsion, caractérisé en ce qu'on ajoute au mélange eau/huile/tensioactif un additif qui est un copolymère séquencé AB avec une séquence A hydrosoluble et une séquence B non hydrosoluble.
  3. Procédé de stabilisation de la plage de température de la zone à une seule phase pour les mélanges eau/huile/tensioactif en microémulsion auxquels un additif est ajouté, dans lequel l'additif ajouté aux mélanges eau/huile/tensioactif est un copolymère séquencé AB avec une séquence hydrosoluble A et une séquence non hydrosoluble B.
  4. Procédé de réduction de la tension de surface de mélanges huile/eau qui contiennent des tensioactifs sous forme de microémulsion, caractérisé en ce qu'on ajoute aux mélanges huile/eau/tensioactif un additif qui est un copolymère séquencé avec une séquence A hydrosoluble et une séquence B non hydrosoluble.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le copolymère séquencé ajouté est un composé avec une structure sur le modèle AB, ABA ou BAB.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'on utilise une séquence B liposoluble et soluble dans les hydrocarbures aliphatiques.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la séquence A a une masse moléculaire comprise entre 500 u et 60 000 u.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la séquence B a une masse moléculaire comprise entre 500 u et 60 000 u.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la séquence A employée est un oxyde de polyéthylène (PEO).
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que la séquence B employée est un polydiène ou un polydiène au moins partiellement hydrogéné.
  11. Procédé selon la revendication 10, caractérisé en ce que la séquence B comprend comme chaínes latérales au moins un élément des groupes méthyl, éthyl, phényl et vinyl.
  12. Microémulsion contenant un mélange eau/huile/tensioactif ainsi qu'un additif, caractérisée en ce que l'additif est un copolymère séquencé AB avec une séquence A hydrosoluble et une séquence B non hydrosoluble.
  13. Microémulsion selon la revendication 12, caractérisée en ce que la séquence B insoluble dans l'eau est soluble dans les hydrocarbures aliphatiques et les huiles minérales.
  14. Microémulsion selon la revendication 12 ou 13, caractérisée en ce qu'elle contient comme additif un copolymère séquencé AB avec une structure selon le modèle ABA ou BAB.
  15. Microémulsion selon l'une quelconque des revendications 12 à 14, caractérisée en ce que la séquence A a une masse moléculaire comprise entre 500 u et 60 000 u.
  16. Microémulsion selon l'une quelconque des revendications 12 à 15, caractérisée en ce que la séquence B a une masse moléculaire comprise entre 500 u et 60 000 u.
  17. Microémulsion selon l'une quelconque des revendications 12 à 16, caractérisée en ce que la séquence A est un oxyde de polyéthylène.
  18. Microémulsion selon l'une quelconque des revendications 12 à 17, caractérisée en ce que la séquence B est un polydiène ou un polydiène au moins partiellement hydrogéné.
  19. Microémulsion selon la revendication 18, caractérisée en ce que la séquence B comprend comme chaínes latérales au moins un élément du groupe méthyl, éthyl, benzyl et vinyl.
  20. Microémulsion selon l'une quelconque des revendications 12 à 19, caractérisée en ce qu'elle est un adjuvant dans une matière.
EP99953661.8A 1998-08-28 1999-08-26 Procede d'augmentation de l'efficacite de tensioactifs et de suppression simultanee de mesophases smectiques, ainsi que tensioactifs auxquels a ete ajoute un additif Expired - Lifetime EP1109883B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19839054 1998-08-28
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
PCT/DE1999/002748 WO2000012660A2 (fr) 1998-08-28 1999-08-26 Procede d'augmentation de l'efficacite de tensioactifs et de suppression simultanee de mesophases smectiques, ainsi que tensioactifs auxquels a ete ajoute un additif

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EP1109883A2 EP1109883A2 (fr) 2001-06-27
EP1109883B1 true EP1109883B1 (fr) 2004-10-27
EP1109883B2 EP1109883B2 (fr) 2014-09-03

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

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WO2006060993A1 (fr) * 2004-12-08 2006-06-15 Forschungszentrum Jülich GmbH Procede pour augmenter l'efficacite de tensioactifs et d'emulsifiants au moyen d'additifs
EP2223995B1 (fr) 2007-09-19 2018-03-07 intelligents fluids GmbH Produit de nettoyage pour la suppression de couches de couleurs de surfaces, procédé de fabrication du produit et procédé de nettoyage

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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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WO2006060993A1 (fr) * 2004-12-08 2006-06-15 Forschungszentrum Jülich GmbH Procede pour augmenter l'efficacite de tensioactifs et d'emulsifiants au moyen d'additifs
EP2223995B1 (fr) 2007-09-19 2018-03-07 intelligents fluids GmbH Produit de nettoyage pour la suppression de couches de couleurs de surfaces, procédé de fabrication du produit et procédé de nettoyage

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WO2000012660A2 (fr) 2000-03-09
US7468349B2 (en) 2008-12-23
WO2000012660A3 (fr) 2000-06-22
DE19839054A1 (de) 2000-03-02
EP1109883A2 (fr) 2001-06-27
US20040054064A1 (en) 2004-03-18
US6677293B1 (en) 2004-01-13
DE59910950D1 (de) 2004-12-02
JP2002525392A (ja) 2002-08-13
ATE280821T1 (de) 2004-11-15
JP4703852B2 (ja) 2011-06-15
EP1109883B2 (fr) 2014-09-03

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