EP1109883B2 - Method for increasing the efficiency of surfactants with simultaneous suppression of lamellar mesophases and surfactants with an additive added thereto - Google Patents
Method for increasing the efficiency of surfactants with simultaneous suppression of lamellar mesophases and surfactants with an additive added thereto Download PDFInfo
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- 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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- 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
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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
- 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
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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
- 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
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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
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.
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Effizienzsteigerung von Tensiden bei simultaner Unterdrückung lamellarer Mesophasen insbesondere in Mikroemulsionen und Emulsionen, sowie Tenside, welchen ein Additiv beigemischt ist.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.
Emulsionen und Mikroemulsionen werden nach dem Stand der Technik durch nichtionische, anionische oder kationische Tenside stabilisiert. Die Tenside vermögen ein unpolares Lösungsmittel (Öl) in einem polaren Lösungsmittel ( z.B. Wasser) oder Wasser in Öl zu solubilisieren. Die Effizienz der Tenside wird in der Menge Tensid ausgedrückt, welche benötigt wird, um einen bestimmten Anteil Öl im Wasser oder umgekehrt zu solubilisieren. Man unterscheidet bei Wasser-Öl-Tensid-Mischungen zusätzlich zwischen Emulsionen und Mikroemulsionen. Während Mikroemulsionen thermodynamisch stabil sind, sind Emulsionen thermodynamisch instabil und zerfallen. Im mikroskopischen Bereich spiegelt sich dieser Unterschied darin wieder, daß die emulgierten Flüssigkeiten in Mikroemulsionen in kleinere Flüssigkeitsvolumina ( z.B. 10-15 µl) gefaßt sind als in Emulsionen (z.B. 10-12 µl). Thermodynamisch instabile Emulsionen weisen somit größere Strukturgrößen auf.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. In the case of water-oil-surfactant mixtures, a distinction is additionally made between emulsions and microemulsions. While microemulsions are thermodynamically stable, emulsions are thermodynamically unstable and disintegrate. At the microscopic level, this difference is reflected in the fact that the emulsified liquids in microemulsions in smaller volumes of liquid (
In Mikroemulsionssystemen können lamellare Mesophasen auftreten. Lamellare Mesophasen führen zu optischer Anisotropie und erhöhter Viskosität. Diese Eigenschaften sind z.B. für Waschmittel unerwünscht, da die lamellaren Mesophasen nicht auswaschbar sind.
Weiterhin beeinflussen Additive im Allgemeinen das Temperaturverhalten der Emulsionen und Mikroemulsionen. So ist im Phasendiagramm eine Verlagerung der Einphasengebiete für Öl-Wasser-Tensid-Mischungen in andere Temperaturbereiche zu beobachten, wenn ein Additiv zugegeben wird. Die Verschiebungen können in der Größenordnung von 10°C liegen. Dies hat jedoch zur Folge, daß z.B. Waschmittelrezepturen geändert werden müssen, um sie dem sich jeweils neu einstellenden Temperaturverhalten des Einphasengebietes anzupassen.
Zusätzlich besteht das Bedürfnis, unter Einsparung von Tensiden ein mindestens gleich gutes Emulgierungsverhalten zu erlangen und die Grenzflächenspannung zu verkleinern, das bedeutet, beispielsweise die Waschkraft von Waschmitteln zu verbessern.In microemulsion systems lamellar mesophases can occur. Lamellar mesophases lead to optical anisotropy and increased viscosity. These properties are undesirable for detergents, for example, since the lamellar mesophases are not washable.
Furthermore, additives generally affect the temperature behavior of the emulsions and microemulsions. Thus, 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. However, this has the consequence that, for example, detergent formulations must be changed in order to adapt to the newly adjusting temperature behavior of the single-phase region.
In addition, there is a need to achieve at least as good emulsifying behavior while saving surfactants and to reduce the interfacial tension, that is, for example, to improve the detergency of detergents.
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Es ist daher die Aufgabe der Erfindung, die Effizienz von Tensiden zu steigern. Weiterhin soll das Auftreten von lamellaren Phasen in Mikroemulsionen bzw. Wasser-, Öl-, Tensidgemischen unterdrückt werden. Das Temperaturverhalten der Emulsionen und Mikroemulsionen soll durch Zugabe des Additivs unbeeinflußt bleiben, das heißt, die Lage des Einphasengebietes im Phasendiagramm soll durch Zugabe der Additive bezüglich der Temperatur im wesentlichen nicht beeinflußt werden. Es soll ein Additiv geschaffen werden, welches die Lage des Einphasengebietes bezüglich der Temperatur nicht beeinflußt. Es soll ebenfalls ein Additiv zur Verfügung gestellt werden, welches die oben genannten Vorteile hat und z.B. einem Waschmittel zugemischt werden kann ohne daß eine Rezepturänderung der verbleibenden Waschmittelrezeptur vorgenommen werden muß. Es soll eine Möglichkeit geschaffen werden, Mikroemulsionen herzustellen, deren Größe der emulgierten Flüssigkeitsteilchen denen von Emulsionen entsprechen.It is therefore 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.
Überraschenderweise werden die Aufgaben, ausgehend vom Oberbegriff des Anspruchs 1, erfindungsgemäß dadurch gelöst, dass als Additiv ein AB-Blockcopolymer mit einem wasserlöslichen Block A und einem wasserunlöslichen Block B zugegeben wird, wobei als Block A des AB Blockcopolymers ein Polyethylenoxid (PEO) eingesetzt wird und als Block B des AB Blockcopolymers ein Polydien oder ein mindestens teilweise hydriertes Polydien eingesetzt wird und ausgehend vom Oberbegriff des Anspruchs 2 dadurch gelöst, dass dem Wasser-Öl-Tensidgemisch als Additiv ein AB Blockcopolymer mit einem wasserlöslichen Block A und einem wasserunlöslichen Block B zugegeben wird, wobei die Blöcke A und B ein Molekulargewicht zwischen 500-5000 g/mol aufweisen. Gemäß Anspruch 3 wird die Aufgabe erfindungsgemäß dadurch gelöst, dass einem Öl-Wasser-Tensidgemisch in Mikroemulsionen als Additiv ein AB-Blockcopolymer mit einem wasserlöslichen Block A und einem wasserunlöslichen Block B zugegeben wird, wobei die Blöcke A und B ein Molekulargewicht zwischen 500-5000 g/mol aufweisen.Surprisingly, the objects, starting from the preamble of
Erfindungsgemäß wird durch die Zugabe des AB-Blockcopolymers zur Wasser-Öl-Tensid-Mischung die Lage des einphasigen Gebietes im Phasendiagramm im Temperaturgebiet nicht verändert, die Effizienz der Tensidmischung wird erheblich gesteigert, lamellare Mesophasen werden in Mikroemulsionen unterdrückt.According to the invention, 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.
Außerdem behalten Mikroemulsionen ihre für sie charakteristischen Eigenschaften unter Vergrößerung ihrer Strukturgröße; so nehmen die emulgierten Strukturen Größen von bis zu ca. 2000 Angström an. Somit wird eine Mikroemulsion erhalten, die die Strukturgrößen einer Emulsion hat, aber thermodynamisch stabil ist. Die Größe der emulgierten Flüssigteilchen hängt von der Temperatur und der zugesetzten Menge Blockcopolymer, bzw. damit von der Zusammensetzung des Tensidgemisches, ab.In addition, microemulsions retain their characteristic properties while increasing their structure size; Thus, the emulsified structures take on sizes of up to about 2000 angstroms. Thus, 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.
Vorteilhafte Weiterbildungen der Erfindung sind in den Unteransprüchen angegeben.Advantageous developments of the invention are specified in the subclaims.
Die Blöcke A und B können dabei Molekulargewichte zwischen 500 u und 60000 u annehmen. Als Block A wird bevorzugt ein Polyethylenoxid (PEO)- Block eingesetzt. Jedoch können alle Blöcke A eingesetzt werden, die wasserlöslich sind, so daß sie in Verbindung mit Block B ein Amphiphil bilden. Weiterhin können für den Block A beispielhaft Polyacrylsäure, Polymethacrylsäure, Polystyrolsulfonsäure sowie deren Alkalimetallsalze, bei denen mindestens teilweise eine Substitution der Säurefunktion durch Alkalimetallkationen erfolgt ist, Polyvinylpyridin und Polyvinylalkohol, Polymethylvinylether, Polyvinylpyrrolidin, Polysaccharide sowie deren Gemische genannt werden.
Für den Block B kommen verschiedene wasserunlösliche Komponenten des genannten Molekulargewichts zum Einsatz. So kann Block B das Produkt einer anionischen 1,2-, 3,4- Polymerisation, bzw. 1,4 Polymerisation von Dienen sein. In Folge kann Block B weiterhin das Produkt einer mindestens teilweisen Hydrierung der Polydiene sein. Als typische monomere Bestandteile kommen 1,3 Butadien, Isopren, alle Konstitumere des Dimethylbutadien, 1,3 Pentadien, 2,4 Hexadiene, α Methylstyrol, Isobutylen, Ethylen, Propylen, Styrol oder Alkylacrylate und Alkylmethacrylate wobei die Alkylgruppe zwischen 2 und 20 Kohlenstoffatome enthält zum Einsatz. Block B kann auch Polydimethylsiloxan sein. Als Block B kann das Polymerisat eines einzigen Monomers oder eines Monomerengemisches verwendet werden.
Block B kann als Seitenketten Methyl-, Ethyl-, Vinyl-Phenyl- oder Benzylgruppen aufweisen.
Die Doppelbindungen in der Polydienkette sowie in den Vinylgruppen, die als Seitenkette existieren können, können entweder ganz oder teiweise hydriert sein. Jedoch kann erfindungsgemäß jedes genügend amphiphile Blockcopolymer eingesetzt werden. Die erfindungsgemäß eingesetzten AB-Blockcopolymere können vorzugsweise aus einer anionischen Polymerisation erhalten werden.
Bei geringeren Molekulargewichten der Blöcke A und B in einer Größenordnung von ca 500-5000 g/mol für die Blöcke A und B werden besonders vorteilhafte Eigenschaften der erfindungsgemäßen AB-Blockcopolymere in Anwendungsprodukten beobachtet. So lösen sich die Polymere mit diesen niedrigen Molekulargewichten schnell und gut auf. Dies gilt zum Beispiel für Lösungen in Seifen und Waschmitteln.The blocks A and B can assume molecular weights between 500 and 60,000 u. As block A, a polyethylene oxide (PEO) block is preferably used. However, all blocks A that are water-soluble may be used so that they form an amphiphile in conjunction with block B. Furthermore, 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.
For block B, various water-insoluble components of said molecular weight are used. Thus, block B may be the product of anionic 1,2-, 3,4-, or 1,4-polymerization of dienes. As a result, 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, α-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. As the 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. However, according to the invention, 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. Thus, the polymers with these low molecular weights dissolve quickly and well. This applies, for example, to solutions in soaps and detergents.
In den erfindungsgemäß eingesetzten AB-Blockcopolymeren sollen die beiden Blöcke A und B ein möglichst hohen Unterschied in ihrer Polarität aufweisen. Dabei soll Block A möglichst polar sein und Block B möglichst unpolar. Hierdurch wird das amphiphile Verhalten gesteigert. Block A soll wasserlöslich sein und Block B soll in unpolaren Medien löslich sein. Vorteilhafterweise ist Block B in Mineralölen oder aliphatischen Kohlenwasserstoffen bzw. in Mineralölen und aliphatischen Kohlenwasserstoffen löslich. Dies gilt auch bei Raumtemperatur.
Weiterhin können auch AB-Blockcopolymere des Typs ABA und BAB einegesetzt werden, die als Triblockcopolymere bezeichnet werden.In the AB block copolymers used according to the invention, the two blocks A and B should have the greatest possible difference in their polarity. 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. Advantageously, block B is soluble in mineral oils or aliphatic hydrocarbons or in mineral oils and aliphatic hydrocarbons. This also applies at room temperature.
Furthermore, it is also possible to use AB block copolymers of the type ABA and BAB, which are referred to as triblock copolymers.
Beispielhaft können folgende Tenside (C) und deren Gemische mit den erfindungsgemäßen Additiven verwendet werden:
- nichtionische Tenside der Klasse Alkylpolyglycolether (CiEj) mit i ≥ 8 (C = C-Atome in der Alkylkette, E = Ethylenoxideinheiten)
- nichtionische Tenside der Klasse Alkylpolyglucoside (APG) "Zuckertenside",CiGj mit i ≥ 8) mit Cotensid Alkohol (Cx-OH, x ≥ 6)
- anionische Tenside, z.B. AOT (Natrium bis (2-ethylhexyl)sulfosuccinat)
- kationische Tenside
- Tensidgemische
- technische Tenside
- nonionic surfactants of the class alkyl polyglycol ethers (C i E j ) with i ≥ 8 (C = C atoms in the alkyl chain, E = ethylene oxide units)
- nonionic surfactants of the class alkyl polyglucosides (APG) "sugar surfactants", C i G j with i ≥ 8) with cosurfactant alcohol (C x -OH, x ≥ 6)
- anionic surfactants, eg AOT (sodium bis (2-ethylhexyl) sulfosuccinate)
- cationic surfactants
- surfactant mixtures
- technical surfactants
Im Folgenden sollen einige Begriffe definiert werden:
- C = Ein beliebiges Tensid, wie anionisches, kationisches, nichtionisches Tensid oder Zuckertensid, sowie deren Gemische, die mindestens zwei Tenside enthalten. D = Additiv, welches dem Tensid C erfindungsgemäß zugefügt wird.
- γ = Gesamttensidkonzentration (Massenbruch) aus C und
- D mit
- m = Masse in g.
- γ = dimensionsloser Massenbruch
- mges = Gesamtmasse aus mwasser + mÖl + m (C) + m (D)
- = Gesamttensidkonzentration am Kreuzungspunkt, an dem im Phasendiagramm das einphasige auf das dreiphasige Gebiet trifft. Dies entspricht der bei gegebenen Wasser/Öl-Verhältnis minimal zur vollständigen Solubilierung von Wasser und Öl notwendigen Gesamttensidkonzentration.
- δ = Massenbruch des Additivs D im Gemisch Tensid C + Additiv D, entspricht
- mit m = Masse in g und
- δ = Massenbruch (dimensionslos)
- C = Any surfactant, such as anionic, cationic, nonionic or sugar surfactant, and mixtures thereof containing at least two surfactants. D = additive which is added to the surfactant C according to the invention.
- γ = total surfactant concentration (mass fraction) from C and
- D with
- m = mass in g.
- γ = dimensionless mass fraction
- m ges = total mass of m water + m oil + m (C) + m (D)
- = Total surfactant concentration at the crossing point where the phase diagram meets the single-phase to the three-phase region. This corresponds to the total surfactant concentration required for the complete solubilization of water and oil given the minimum water / oil ratio.
- δ = mass fraction of the additive D in the mixture of surfactant C + additive D, corresponds
- with m = mass in g and
- δ = mass fraction (dimensionless)
Im Folgenden soll die Erfindung beispielhaft erläutert werden.In the following, the invention will be explained by way of example.
PX/Y = Additiv mit einem Molekulargewicht in 1000g/mol X an hydrophober Alkylkette (hydriertes 1,4-Polyisopren) und einem Molekulargewicht in 1000g/mol Y an Polyethylenoxid.
Beispiel P5/5 : die Alkylkette hat ein Molekulargewicht von 5000 g/mol (= u) und die Polyethylenoxidkette hat ein Molekulargewicht von 5000 g/mol.
P22/15: die Alkylkette hat ein Molekulargewicht von 22000 g/mol und die Polyethylenoxidkette hat ein Molekulargewicht von 15000 g/mol.
Die auf diese Weise dargestellten Additive sind AB-Blockcopolymere.
Die hier beispielhaft dargestellten Verbindungen können nach dem Herstellungsverfahren aus der
Example P5 / 5: the alkyl chain has a molecular weight of 5000 g / mol (= μ) and the polyethylene oxide chain has a molecular weight of 5000 g / mol.
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
Das Verhalten der erfindungsgemäßen Mikroemulsionen ist in den Figuren dargestellt:
-
Fig.1 : Typischer Temperatur/Tensidkonzentrationsschnitt durch das Phasenprisma bei konstantem Wasser/Öl-Verhältnis für das H2O-Tetradekan-C6E2-System zum Vergleich. -
Fig.2 : Die Einphasengebiete für das Gemisch Wasser/n-Dekan-C10E4-P5/5 als Funktion der Zugabe P5/5 (δ) in einem Temperatur/Tensidkonzentrationsdiagramm. -
Fig.3 : Die Einphasengebiete für das Gemisch Wasser/n-Dekan-C10E4-P10/10 als Funktion der Zugabe P10/10 (δ) in einem Temperatur/Tensidkonzentrationsdiagramm. -
Fig.4 : Die Einphasengebiete für das Gemisch Wasser/n-Dekan-C10E4-P22/22 als Funktion der Zugabe P22/22 (δ) in einem Temperatur/Tensidkonzentrationsdiagramm. -
Fig.5 : Die Einphasengebiete für das Gemisch Wasser/n-Dekan-C10E4-P5/3 als Funktion der Zugabe P5/3 (δ) und P5/2 (δ) in einem Temperatur/Tensidkonzentrationsdiagramm. -
Fig.6 : Die Einphasengebiete für das Gemisch Wasser/n-Dekan-C10E4-P22/15 als Funktion der Zugabe P22/15 (δ) in einem Temperatur/Tensidkonzentrationsdiagramm. -
Fig.7 : Die Einphasengebiete für das Gemisch Wasser/n-Dekan-C10E4-P5/15 und Wasser/n-Dekan-C10E4-PI5/PEO15 (PI5 = Polyisopren mit Molekulargewicht 5000g/mol, PEO15 = Polyethylenoxyd mit Molekulargewicht 15000 g/mol (AB-Blockcopolymer).) als Funktion der Zugabe δ in einem Temperatur/Tensidkonzentrationsdiagramm. -
Fig.8 : Die Einphasengebiete für das Gemisch Wasser/n-Dekan-C10E4-P5/30 als Funktion der Zugabe P5/30 (δ) in einem Temperatur/Tensidkonzentrationsdiagramm. -
Fig.9 : Die Einphasengebiete für das Gemisch (Wasser+NaCl)/n-Dekan-AOT-P5/5 als Funktion der Zugabe P5/5 (δ) in einem Temperatur/Tensidkonzentrationsdiagramm. -
Fig.10 : Die Einphasengebiete für das Gemisch Wasser/n-Oktan-Oktanol-C8G1-P5/5 (C8G1 = n-octyl-β-D-Glucopyranosid, welches ein Zuckertensid ist) als Funktion der Zugabe P5/5 (δ) in einem Tetraederschnitt bei einem konstantem Wasser/Öl-Verhältnis und T=25°C. C8G1 ist hierbei ein Zuckeramphiphil. -
Fig.11 : Übersicht: als Funktion von δ für die verschiedenen Wasser/n-Dekan-C10E4-Px/y-Systeme. -
Fig.12 Einphasengebiete für die Systeme H2O-n-Dekan-C10E4- P22/22 (leere Kreise) und H2O-n-Dekan-C10E4-P1/1 (schwarze Rauten) in Abhängigkeit von δ. -
Fig.13 : Einphasengebiete für die Systeme H2O-Cyclohexan-C8E4- PS1/PEO1 (PS1 = Polystyrol mit Molekulargewicht 1000g/mol, PEO1 = Polyethylenoxid mit Molekulargewicht 1000g/mol ; (AB-Blockcopolymer)) in einem Temperatur/Tensidkonzentrationsdiagramm. Das Verhältnis H2O/Cyclohexan ist 1:1.
-
Fig.1 : Typical temperature / surfactant concentration section through the phase prism at constant water / oil ratio for the H 2 O-tetradecane C 6 E 2 system for comparison. -
Fig.2 : The single-phase ranges for the mixture water / n-decane C 10 E 4 -P5 / 5 as a function of the addition P5 / 5 (δ) in a temperature / Tensidkonzentrationsdiagramm. -
Figure 3 : The single-phase ranges for the mixture water / n-decane C 10 E 4 -P 10/10 as a function of the addition of P10 / 10 (δ) in a temperature / surfactant concentration diagram. -
Figure 4 : The single-phase ranges for the mixture water / n-decane C 10 E 4 -P22 / 22 as a function of addition P22 / 22 (δ) in a temperature / surfactant concentration diagram. -
Figure 5 : The single-phase ranges for the mixture water / n-decane C 10 E 4 -P5 / 3 as a function of the addition of P5 / 3 (δ) and P5 / 2 (δ) in a temperature / surfactant concentration diagram. -
Figure 6 : The single-phase ranges for the mixture water / n-decane C 10 E 4 -P22 / 15 as a function of addition P22 / 15 (δ) in a temperature / surfactant concentration diagram. -
Figure 7 : The single phase ranges for the mixture water / n-decane C 10 E 4 -P5 / 15 and water / n-decane C 10 E 4 -PI5 / PEO15 (PI5 = polyisoprene with molecular weight 5000g / mol, PEO15 = polyethylene oxide with molecular weight 15000 g / mol (AB block copolymer).) As a function of the addition δ in a temperature / surfactant concentration diagram. -
Figure 8 : The single-phase ranges for the mixture water / n-decane C 10 E 4 -P5 / 30 as a function of addition P5 / 30 (δ) in a temperature / surfactant concentration diagram. -
Figure 9 : The single-phase areas for the mixture (water + NaCl) / n-decane-AOT-P5 / 5 as a function of addition P5 / 5 (δ) in a temperature / surfactant concentration diagram. -
Figure 10 : The single phase regions for the mixture of water / n-octane-octanol C 8 G 1 -P5 / 5 (C 8 G 1 = n-octyl-β-D-glucopyranoside, which is a sugar surfactant) as a function of addition P5 / 5 (δ) in a tetrahedral section at a constant water / oil ratio and T = 25 ° C. C 8 G 1 is a sugar amphiphile. -
Figure 11 : Overview: as a function of δ for the various water / n-decane C 10 E 4 Px / y systems. -
Figure 12 Single phase regions for the systems H 2 on decane C 10 E 4 - P22 / 22 (open circles) and H 2 on decane C 10 E 4 -P1 / 1 (black diamonds) as a function of δ. -
Figure 13 : Single Phase Areas for the Systems H 2 O-cyclohexane C 8 E 4 - PS1 / PEO1 (PS1 = polystyrene with molecular weight 1000g / mol, PEO1 = polyethylene oxide with molecular weight 1000g / mol (AB block copolymer)) in a temperature / surfactant concentration diagram. The ratio H 2 O / cyclohexane is 1: 1.
Die in den
Dabei ist die Temperatur T gegen die Gesamttensidkonzentration γ für das System Wasser/n-Tetradecan-C6E2 und ein Wasser/n-Tetradekan-Verhältnis von 1:1 aufgetragen. Bei höheren Tensidkonzentrationen befindet sich das Einphasengebiet 1 des Gemisches. An diesen Gebiet schließt sich in Richtung kleinerer Tensidkonzentrationen ein geschlossenes Dreiphasengebiet 3 an. Oberhalb und unterhalb der Phasengrenzlinien befinden sich Zweiphasengebiete 2. Der Punkt, an dem alle Phasengebiete zusamnmentreffen, wird durch die Tensidkonzentration und die Temperatur definiert. Je mehr zu kleinen Werten verschoben ist, desto größer ist die Strukturgröße der Mikroemulsionen.The temperature T is plotted against the total surfactant concentration γ for the system water / n-tetradecane-C 6 E 2 and a water / n-tetradecane ratio of 1: 1. At higher surfactant concentrations is the
Die in den
In diesen Diagrammen sind Kurven zu jeweils einem δ - Wert eingezeichnet, welche die Begrenzung des jeweiligen zu einem δ-Wert gehörigen Einphasengebiet charakterisiert. Die Spitze der jeweiligen Kurve ist derjenige Punkt, an dem verschiedene Mehrphasengebiete zusammentreffen. Je weiter die Spitze einer Kurve bei niedrigeren Tensidkonzentrationen, d.h. γ - Werten, angesiedelt ist, desto größer ist die Effizienz des Tensids C durch die Zugabe des Blockcopoymeren D.In these diagrams, curves are plotted, each with a δ value, which characterizes the limitation of the respective single-phase region belonging to a δ 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 γ values, the greater the efficiency of the surfactant C by the addition of the block copolymer D.
In
Die Effizienz des Gesamttensids wird auch in dem in
In
In
In
Während in den
Um die Effizienzsteigerung der Blockcopolymere für eine weitere Tensidklasse zu dokumentieren, ist in
While in the
In order to document the increase in efficiency of the block copolymers for a further class of surfactants, is in
Im Gegensatz zu konventionellen Tensidmischungen führt bei den Blockcopolymeren schon eine sehr geringe Zugabe δ zu einem stärkeren Absinken von , und damit zu starker Effizienzsteigerung.
In contrast to conventional surfactant mixtures, a very small addition of δ leads to a greater decrease in the block copolymers , and therefore to greater efficiency.
Der Wert des Wasser/Öl-Grenzflächenspannungsminimums korreliert mit der Effizienz der Tensidmischung, wobei z.B. für den Waschprozeß eine möglichst niedrige Grenzflächenspannung erwünscht ist.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.
In
Die Messungen in
Mit den erfindungsgemäß eingesetzten AB Blockcopolymeren wird das Auftreten lammelarer Mesophasen wird unterdrückt. Das Temperaturverhalten der Mikroemulsionen bleibt unverändert, das heißt die Lage des Einphasengebietes bezüglich der Temperatur im Phasendiagramm wird durch die Zugabe der erfindungsgemäß eingesetzten Additive nicht beeinflußt. Daher muß die Rezeptur eines Waschmittels nicht verändert werden um eine gleichbleibende Lage des Einphasengebietes bezüglich der Temperatur im Einphasendiagramm zu bewirken.
Die erfindungsgemäßen AB-Blockcopolymere können nicht nur in Waschmitteln eingesetzt werden; sie können mit derselben Wirkung auch beispielsweise als Zusätze in Lebensmitteln und Kosmetika sowie in allen industriellen oder technischen Anwendungen von Mikroemulsionen und Emulsionen, z.B. beim Einsatz in der Erdölförderung, in der Bodensanierung sowie bei der Anwendung als z.B. Reaktionsmedium verwendet werden.
Die mittels der erfindungsgemäßen Zugabe der AB Blockcopolymere hergestellten Mikroemulsionen weisen emulgierte Flüssigkeitsvolumina auf, deren Größe denen von Emulsionen entsprechen.
Die erfindungsgemäßen Wirkungen können durch jeden gemeinsamen Einsatz eines Tensids mit dem AB-Blockcopolymer in einem zu emulgierenden System erreicht werden. Ein Tensid, welchem ein erfindungsgemäßes AB-Blockcopolymer beigefügt ist, sowie jedes damit emulgierte System umfassend zusätzlich Wasser und/oder Öl sind daher von der Erfindung umfaßt.
Die erfindungsgemäßen Wirkungen beschränken sich nicht auf Emulsionen und Mikroemulsionen, sondern beeinflussen das Verhalten von Tensiden im allgemeinen in der beschriebenen Weise.With the AB block copolymers used according to the invention, 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.
Claims (10)
- A method of increasing the efficiency of surfactants in a microemulsion consisting of water and oil by the addition of additives having a water-soluble and a water-insoluble component, characterized in that, as additive, an AB block copolymer with a water-soluble block A and a water-insoluble block B is added, a polyethylene oxide (PEO) being used as block A of the AB block copolymer and a polydiene or an at least partially hydrogenated polydiene being used as block B of the AB block copolymer.
- A method of suppressing lamellar phases in water/oil/surfactant mixtures which are present in microemulsions, characterized in that an AB block copolymer with a water-soluble block A and a water-insoluble block B is added to the water/oil/surfactant mixture as additive, the blocks A and B having a molecular weight of between 500 and 5000g/mol.
- A method of stabilizing the temperature state of the single-phase region for oil/water/surfactant mixtures in microemulsions to which an additive is added, in which case an AB block copolymer with a water-soluble block A and a water-insoluble block B is added to the oil/water/surfactant mixtures as additive, the blocks A and B having a molecular weight of between 500 and 5000g/mol.
- A method according to one of Claims 1 to 4, characterized in that a compound having the structure according to type AB, ABA or BAB is added as block copolymer.
- A method according to one of Claims 1 to 4, characterized in that a block B is used which is soluble in oil and in aliphatic hydrocarbons.
- A method according to one of Claims 1, 4 or 5, characterized in that block A has a molecular weight of between 500 u and 60000 u.
- A method according to one of Claims 1, or 4 to 6, characterized in that block B has a molecular weight of between 500 u and 60000 u.
- A method according to one of Claims 2 to 7, characterized in that a polyethylene oxide (PEO) is used as block A.
- A method according to one of Claims 2 to 8, characterized in that a polydiene or an at least partially hydrogenated polydiene is used as block B.
- A method according to Claim 9, characterized in that block B has, as side chains, at least one component from the groups consisting of methyl, ethyl, phenyl and vinyl.
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DE19839054 | 1998-08-28 | ||
PCT/DE1999/002748 WO2000012660A2 (en) | 1998-08-28 | 1999-08-26 | Method for increasing the efficiency of surfactants with simultaneous suppression of lamellar mesophases and surfactants with an additive added thereto |
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-
1998
- 1998-08-28 DE DE19839054A patent/DE19839054A1/en not_active Withdrawn
-
1999
- 1999-08-26 US US09/763,413 patent/US6677293B1/en not_active Expired - Fee Related
- 1999-08-26 DE DE59910950T patent/DE59910950D1/en not_active Expired - Lifetime
- 1999-08-26 WO PCT/DE1999/002748 patent/WO2000012660A2/en active IP Right Grant
- 1999-08-26 EP EP99953661.8A patent/EP1109883B2/en not_active Expired - Lifetime
- 1999-08-26 AT AT99953661T patent/ATE280821T1/en active
- 1999-08-26 JP JP2000571065A patent/JP4703852B2/en not_active Expired - Fee Related
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2003
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Also Published As
Publication number | Publication date |
---|---|
WO2000012660A3 (en) | 2000-06-22 |
US20040054064A1 (en) | 2004-03-18 |
DE59910950D1 (en) | 2004-12-02 |
JP2002525392A (en) | 2002-08-13 |
EP1109883A2 (en) | 2001-06-27 |
US7468349B2 (en) | 2008-12-23 |
WO2000012660A2 (en) | 2000-03-09 |
US6677293B1 (en) | 2004-01-13 |
ATE280821T1 (en) | 2004-11-15 |
JP4703852B2 (en) | 2011-06-15 |
EP1109883B1 (en) | 2004-10-27 |
DE19839054A1 (en) | 2000-03-02 |
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