WO1995014076A1 - Concentrated surfactant compositions - Google Patents
Concentrated surfactant compositions Download PDFInfo
- Publication number
- WO1995014076A1 WO1995014076A1 PCT/EP1994/003726 EP9403726W WO9514076A1 WO 1995014076 A1 WO1995014076 A1 WO 1995014076A1 EP 9403726 W EP9403726 W EP 9403726W WO 9514076 A1 WO9514076 A1 WO 9514076A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- surfactant
- weight
- phase
- composition
- Prior art date
Links
Classifications
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/886—Ampholytes containing P
-
- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
-
- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/92—Sulfobetaines ; Sulfitobetaines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
Definitions
- the present invention relates to novel, concentrated aqueous surfactant compositions, in particular to amphoteric surfactant compositions which are mobile or pumpable at high concentrations of active ingredient. Such compositions are prepared in the presence of a phase modifier, thus allowing the preparation of such compositions over a wider range of active concentrations than has hitherto been possible. More specifically, the present invention relates to a novel method for the production of particular concentrated amphoteric surfactant compositions, especially betaines and fatty imidazoline derivatives, wherein preparation of such surfactants or surfactant compositions utilises a non-surfactant organic solvent as a phase modifier.
- the preferred betaines according to the present invention are N-carboxymethylated derivatives of tertiary amine intermediates possessing at least one fatty alkyl chain e.g. cocoamido propyl betaine (CAPB) , sulphobetaines, phosphobetaines, and hydroxysulphobetaines, and N-carboxymethylated derivatives of amidoamines e.g. produced by the hydrolysis of imidazolines and especially of imidazolines having an alkyl and a hydroxyalkyl chain e.g. N-carboxymethylated lauric hydroxyethyl imidazoline (CL-HI) .
- CAPB cocoamido propyl betaine
- sulphobetaines phosphobetaines
- hydroxysulphobetaines e.g. N-carboxymethylated derivatives of amidoamines e.g. produced by the hydrolysis of imidazolines and especially of imidazolines having an alkyl and
- Amphoteric surfactants incorporate electropositive and electronegative elements in the same molecule, allowing for the formation of salts in either acidic or alkaline conditions. Amphoteric surfactants are generally gentle on the skin and eyes, exhibit low toxicity, and are very effective as mild surfactants. Furthermore, developments in the detergent and personal hygiene product areas have become increasingly focused on derivatives of naturally- occurring raw materials, such as natural fats and oils, because of the environmental and toxicological advantages such derivatives offer over more conventional raw feedstocks.
- Surfactant compositions are prepared and sold for a wide variety of industrial and domestic applications. They are often required in a fluid form, and it is therefore often desirable that they should contain as high a proportion of active material as possible, whilst retaining mobility in order to reduce the costs of storage and transport.
- the surfactant composition has a melting point below, or only slightly above ambient temperature it is sometimes possible to supply the surfactants in the form of an anhydrous composition, or a composition containing up to about 5% of water, respectively. In the latter case the trace of water appears to act as a melting point depressor.
- a composition of the surfactants according to the present invention is prepared in aqueous solutions of increasing concentration, the molecules are first found to associate in spherical clusters (micelles) , which with increasing concentrations become rod-like. With increasing concentration, the micelles become more crowded, resulting in a rise in the viscosity of the solution and, with the great majority of cases, said micelles eventually lengthening to form a regular hexagonal array of cylindrical surfactant micelles in an aqueous medium, usually referred to as the rigid "M 1 " liquid crystal phase.
- a phase change occurs to produce either a hydrated solid phase, or, in the case of certain surfactant mixtures containing one or more surfactants of this invention, to convert the M phase progressively to a fluid "G" phase until a viscosity minimum is reached. Further increasing the concentration of the "G” phase results in an increase in viscosity, and ultimately to a further phase change, producing either an hydrated solid or a second immobile liquid crystal phase (the M phase) which resembles the M phase in structure, but wherein the structure is inverted - i.e. with water as the internal phase and the surfactant as the continuous phase.
- hydrated solid phase has been used broadly to include those systems which comprise suspensions of solid or immobile gel phases in one or more viscous or gel phase to provide a more or less rigid material usually having a granular appearance under a polarising microscope. No one surfactant has been found which will form all of the various liquid crystal phases.
- Optically isotropic phases do not tend to rotate the plane of polarisation of plane polarised light. If a drop of sample is placed between two sheets of optically plane polarising material whose planes of polarisation are at right angles, and light is shone on one sheet, optically isotropic samples do not appear substantially brighter than their surroundings when viewed through the other sheet. Optically anisotropic materials however appear substantially brighter. Optically anistropic esophases typically show characteristic textures when viewed through a microscope between crossed polarisers, whereas optically isotropic phases usually show a dark, essentially featureless continuum.
- Newtonian liquids have a viscosity which is independent of shear.
- liquids are considered Newtonian if the viscosity does not vary substantially at shear rates up to 1000 -1
- L -phases are mobile, optically isotropic, and typically Newtonian liquids which show no texture under the polarising microscope. Electron microscopy is capable of resolving texture only at very high magnifications.
- the viscosity of an L -phase is usually low, but may rise significantly as the concentration approaches the upper phase boundary. This is believed to reflect a change in the shape of the micelles from spherical to prolate.
- G-phases are pourable, thixotropic, anisotropic products. They are typically viscous-looking, opalescent materials with a characteristic "smeary" appearance on flowing. They form characteristic textures under the polarising microscope.
- M-phases are typically immobile, anisotropic products resembling waxes. They give characteristic textures under the polarising microscope.
- the "G” phase or “L” phase can be located very rapidly and easily, using standard laboratory equipment, by placing a sample of the test composition (at the active concentration estimated to produce a "G” or “L “ phase) on a slide on the block of a heated stage microscope. Examination between crossed polarisers will reveal in which phase the sample is present.
- the various phases each have a characteristic appearance which is easily identified by comparison, for example with the photographs of typical liquid crystal phases in the classic paper by Rosevear, JAOCS Vol 31 P 628 (1954) or in J. Colloid and Interfacial Science, Vol 30 No 4 P 500.
- water may be allowed to evaporate from the edges of the sample under the cover disk and any phase resulting changes observed. If an Mcron phase or hydrated solid is present water may be added around the edge of the cover disks and allowed to diffuse into the composition, both of which may alter the active concentration of the sample under investigation, by an amount sufficient to produce a "G" phase. If no "G" phase is located in this way samples may be heated progressively on the block and the operation repeated.
- active concentration refers to the total concentration of surface active material in the total aqueous surfactant composition.
- amphoteric surfactant compositions A particular requirement exists for mobile, pumpable concentrated aqueous amphoteric surfactant compositions, in order to reduce transport and storage costs. This need is increased by the growing trend towards the use of amphoteric surfactant compositions in applications where mildness is considered an important feature of the surfactant.
- amphoteric surfactants "in situ" to produce a mobile, pumpable, concentrated surfactant composition at high concentrations of active ingredient that hitherto were unattainable.
- compositions would typically have been an immobile gel (M- ⁇ phase) with poor dilution characteristics, causing significant problems in preparation and handling.
- M- ⁇ phase immobile gel
- a ⁇ photeric surfactant coirpositions for example CAPB and CL-HI, have hitherto only been obtainable as liquid compositions at concentrations of less than approximately 30% w/w active ingredient, based on the total weight of the composition.
- concentrations eg. up to about 50% w/w active ingredient
- the coirpositions are typically sticky, very viscous or immobile, and difficult to handle, requiring where possible expensive spray-drying in order to achieve a commercially acceptable powdered product.
- this because of the finely divided nature of the powder, this also presents handling difficulties and, moreover may entail health risks.
- G phase composition will vary according to the particular active ingredients in question "L " phase composition is more likely to be formed in a reaction medium having an excess of water, and a “G” phase composition is more likely to be formed in a reaction medium having an excess of solvent. However, this is only a generalisation, the exact ratio for the reaction medium being dependent upon the active ingredients c ⁇ prising said surfactant system.
- the present invention provides aqueous, mobile, concentrated, amphoteric surfactant compositions, consisting substantially of at least 5% and not more than 45% by weight of water, preferably not more than 40%; at least 30% by weight of amphoteric surfactant, preferably 35 to 70%; and 5 to 45% of a water-miscible, non-surfactant organic solvent, wherein said composition is a "G" phase and the concentration of surfactant in said composition corresponds to that at which the composition can exist, at least predominantly, in the "G" phase.
- the present invention further provides aqueous, mobile, concentrated amphoteric surfactant coirpositions, consisting essentially of at least 5% and not greater than 65% by weight of water, preferably 10% to 60%; at least 25% by weight of amphoteric surfactant, preferably 30% to 70%; 5% to 45% of a water miscible, non-surfactant organic solvent, wherein said composition is an "L " phase.
- amphoteric surfactants may for example comprise a compound of the formula:-
- R is an alkyl, alkenyl, alkyla idoalkyl, al-kenylamidoalkyl, alk(en)yl polyoxyalkylene or alkaryl group having in each case a C Conduct_ C 22
- R- is H or a C, C, straight or branched chain alkyl, alkenyl or hydroxyl group, or may be absent or may be combined with R to form a cyclic group
- X is nitrogen or phosphorus n is from 1 to 3 and A is 000 , SO or PO H .
- composition of the present invention may be prepared by reacting a secondary or tertiary amine:-
- R, R. and R ⁇ are as hereinabove defined, with a carboxymethylating agent in the presence of the appropriate proportions of the non-surfactant water-miscible solvent and water.
- amphoteric surfactant may be a derivative of a fatty imidazoline such as (for example) an N-hydroxyethyl fatty alkyl imidazoline.
- compositions of our invention may be prepared by:
- R, R- , R_ are as hereinabove defined and R is a C- to C alkyl group
- said quaternised amine is subsequently saponified with an aqueous base e.g. sodium hydroxide, to produce the betaine.
- an aqueous base e.g. sodium hydroxide
- the coirpositions of the present invention preferably contain at least 30% by weight of the amphoteric surfactant, preferably at least 33%, e.g. at least 35%, such as 45%, all percentages being based upon the total weight of said composition.
- said betaine a ⁇ photeric surfactants are prepared from alkylamido dimethyl amines, alkyldimethylamines or fatty acid hydroxethyl imidazoline.
- any fatty imidazolines used comprise a C 8 ⁇ C 22 al ⁇ Y 1 group' especially a C 10 - 18 alkyl group, and a C to C hydroxyalkyl group, especially a C -0. hydroxyalkyl group.
- the fatty imidazoline derivatives may be derived from lauryl hydroxyethyl imidazoline.
- the organic solvents used to produce the reaction medium according to the present invention are non-surface active and miscible with water in some or all proportions.
- Organic solvents suitable for use according to the present invention include water soluble onohydric alcohols e.g. C -C monohydric alcohols; water soluble diols e.g. C -C glycols such as ethylene glycol, propylene glycol, and hexylene glycol; water soluble polyglycols e.g. polyethylene glycol and polypropylene glycol; water soluble polyhydric alcohols e.g. glycerol, polyglycerols, and pentaerythritol; water soluble ethoxylated C alcohols, e.g. dipropylene glycol monomethylether.
- water soluble onohydric alcohols e.g. C -C monohydric alcohols
- water soluble diols e.g. C -C glycols such as ethylene glycol, propylene glycol, and hexylene glycol
- water soluble polyglycols e.g. polyethylene glycol and
- Especially preferred organic solvents are propylene glycol, polyethylene glycol, dipropylene glycol monomethy1 ether and/or glycerol.
- the ratio of water-soluble, non-surface active organic solvent:water in said reaction medium is from 1:10 to 10:1, dependent upon the desired phase and viscosity of the resultant surfactant composition.
- Said solvents may be present in the composition in a ratio of solvent: water such that the surfactant is present in an "L " phase or in a "G” phase.
- solvent e.g. 60/40 w/w ratio of propylene glycol:water
- amphoteric surfactants e.g. betaines
- water e.g. a 15/85 w/w ratio of propylene glycol:water
- amphoteric surfactants e.g. imidazoline derivatives
- said solvent is present in said coirposition at levels not exceeding 75%, usually between 5% and 65% based on the total weight of the composition, preferably 7%-40%.
- the percentage of said solvent, and its ratio to water, is adjusted according to the phase behaviour of the particular amphoteric surfactant, to provide a composition comprising essentially amphoteric surfactant, organic solvent and water, said composition being an "L " phase or a "G” phase at ambient temperature.
- the level of reaction medium in the composition is typically greater than 35% by weight and less than 70% by weight of the composition, e.g. 40-65% dependent upon the nature of the active ingredients.
- the coirpositions according to the present invention may be prepared by mixing an appropriate quantity of an amphoteric surfactant, which in the absence of the reaction medium according to the present invention would typically produce an immobile or high viscosity gel, with the correct proportion of water, and water miscible, non-surface active organic solvent, in order to obtain a surfactant composition in the "L " phase, or the "G” phase.
- the composition containing the active ingredients in a phase other than the "G” phase or “L " phase may be prepared by the production of the amphoteric surfactant directly in the solvent/water medium, i.e. in situ. In such cases the proportions of solvent:water in said medium are sufficient to be capable of producing a composition in the "G" phase or "L " phase.
- carboxymethylation agents include those agents such a methyl acrylate, ethyl acrylate, acrylic acid, 2-hydroxy-l,3-propane sultone, 3-chloro-2-hydroxypropane sulphonic acid, 1,3-propane sultone, alkyl chloroacetate, and especially sodium chloroacetate.
- alkylations may be carried out either neat, in inert solvents or, in aqueous solution.
- Any suitable amount of-carboxymethylating agent may be added to the reaction medium, typically being the minimum amount required to substantially carboxylate the amine.
- the carboxylate may be neutralised to produce the amphoteric surfactant by treatment with any suitable neutralising agent, for example alkali or alkaline earth metal hydroxides e.g. NaOH.
- any suitable neutralising agent for example alkali or alkaline earth metal hydroxides e.g. NaOH.
- the temperature of the carboxymethylation reaction may be between ambient and 120°C such that degradation of the amine or the amphoteric surfactant does not occur e.g. 35°C-90°C, especially 50°C-80°C.
- the carboxymethylation reaction may be carried out over a period of 0.5 to 24 hours dependent upon the temperature of the reaction mixture and the degree of carboxymethylation required e.g. 5 to 20 hours, such as 12 to 18 hours.
- reaction mixture may have a 10% aqueous solution pH of 7 to 14, e.g. 9 to 12.5, such as 10 to 12.
- said composition typically has a solids content of 30-60% w/w, e.g. 35-55% and is either an "L " phase or "G” phase dependent upon the reaction medium employed and the active ingredients in question.
- compositions of the present invention whilst being mobile, have a viscosity at ambient temperature such that they may be pumped at a rate sufficient to facilitate easy handling of the coirpositions.
- compositions of the present invention have viscosities in the range 400 to 15,000 centipose (cps), preferably 600 to 7000 cps, most preferably 700 to 6000 cps at ambient temperature.
- compositions of the present invention are pu ⁇ pable at concentrations within a range of + 10%, active ingredient preferably + 5% e.g. + 2.5% of the minimum viscosity concentration. This range tends to be broader at more elevated temperatures.
- the viscosity of compositions of the present invention may be determined by any suitable method e.g. Brookfield Viscometer or controlled shear/stress rhe ⁇ meter.
- compositions of the present invention may contain minor amounts of non-colloidal electrolytes such as sodium chloride or sodium sulphate. Such inclusions may be present as impurities from the feedstocks used during the manufacture of the component, or may be generated as by-products if the surfactant is manufactured in-situ. However, the presence of organic salts or similar non-colloidal electrolyte is undesirable, often resulting in an increase in the viscosity of the fluid "G" phase, and in the case of chloride salts may ultimately lead to problems of corrosion.
- non-colloidal electrolytes such as sodium chloride or sodium sulphate.
- the proportion of non-surface active electrolyte present in the coirpositions of the present invention is below 10% and more preferably below 5% by weight of the active mixture, preferably below 5% by weight of the total compositions.
- the presence of some electrolyte may be useful, e.g. when the melting point of the "G" phase is slightly above ambient temperature, and an increase in the electrolyte content of the coirposition may depress the melting point sufficiently to obtain a pumpable "G" phase without heating.
- a non-colloidal electrolyte e.g. sodium chloride, sodium sulphate, sodium acetate or sodium citrate.
- the coirpositions of our invention may further optionally contain minor amounts, e.g. up to 5% by weight of the active mixture, of surface active material other than those specified herein.
- amphoteric surfactants of the present invention may be formulated into surfactant compositions which may additionally comprise, for example, other surfactants or synergists, antiperspirants, deodorants, lanolin or other skin softening or moisturising preparation, analgesics, antiseptics, emulsifiers, dispersants, soaps, polymeric thickening agents, wetting agents, foam controlling agents, perfumes and colouring.
- surfactant compositions may additionally comprise, for example, other surfactants or synergists, antiperspirants, deodorants, lanolin or other skin softening or moisturising preparation, analgesics, antiseptics, emulsifiers, dispersants, soaps, polymeric thickening agents, wetting agents, foam controlling agents, perfumes and colouring.
- amphoteric surfactants of the present invention are especially suitable for inclusion into the personal care products, where the mild nature of such surfactants is especially desirable.
- Example 1 The preparation of cocoamido propyl betaine (CAPB) in propylene glycol:water 60/40 w/w reaction medium
- CAPB was prepared in-situ in a 60/40 w/w mixture of propylene glycol:water.
- Water 581.6g
- propylene glycol 1556.4g
- 80% aqueous monochloroacetic acid solution 781.2g
- 47% aqueous NaOH solution 394.0g
- coco amidopropyl dimethylamine 2000.Og
- the pH of the reaction mixture was adjusted to 9.0 using NaOH solution (I72.0g), with the reaction mixture being a clear, pale yellow liquid. No viscosity 'hump' characteristic of such preparations not using the reaction medium of the present invention was noted over this initial stage.
- the mixture was further heated at 80°C whilst maintaining the pH between 9.0-9.5 by addition of NaOH solution (100.Og in total) As the reaction progressed, the mixture became increasingly turbid, especially at room temperature, with the mixture eventually becoming properly turbid at 50°C.
- the total reaction time was approximately 20 hours, with one addition of 80% monochloroacetic acid solution (7.5g) being made to lower the free amidoamine content.
- the pH of the final product was lowered to 5.1 by addition of CH SO .
- the product was a mobile, free flowing "G" phase.
- Example 2 The "in situ” Preparation of a Why Imidazoline derivative (CLHL) in 85/15 w/w water:propylene glycol reaction medium
- reaction medium comprising an 391g water and 119g propylene glycol. 21g of 47% NaOH solution was added thereto.
- reaction medium was added, as a carboxymethylating agent, 80% monochloroacetic acid (280g) and subsequently, as a neutralising agent, 47% NaOH (180g) .
- the reaction mixture was maintained at 70°C for 15 hours, and the pH of the reaction mixture was maintained by further addition of 47% NaOH Solution
- the product was a clear, mobile amber coloured liquid with a total ssoolliiddss ccoonntteeint of 50% by weight, being an L phase at ambient temperature.
- propylene glycol (15:85 propylene glycol:water) in the initial charge yielded a product with a similar viscosity to a sample of a conventional carboxymethylated lauric hydroxy ethyl imidazoline derivative prepared in the absence of solvent, with the former having the advantage of a 39% w/w increase in solids content with an identical composition, on a "pro rata" basis.
- Example 4 Concentration and subsequent re-dilution of compositions of Example 2
- Samples of the lauric imidazoline derivative composition of Example 3 were concentrated to 70-80% w/w solids by evaporation of water, and subsequently re-diluted to 50% w/w solids by the addition of mixtures of propylene glycol:water or glycerol:water co-solvents of various ratios.
- phase viscosity at 25°C, 37°C and 45°C and the phase at ambient temperature of the coirpositions were determined.
- IAPB was prepared in situ in a 60:40 w/w mixture of propylene glycol:water.
- a further quantity of 80% w/w aqueous MCA (5.8g; 0.05mol) was added to lower the free amidoamine content, and the mixture was heated for another 20 hours at 80°C and at a pH of 9.0 to 9.5. The pH was lowered by addition of 36% w/w hydrochloric acid and the product cooled to ambient temperature.
- the overall mole ratio lauryl amidopropyl dimethylamine: MCA was 1.00:1.01.
- reaction mixture had the appearance of a clear, highly mobile, pale yellow solution throughout the charging, reaction, and neutralization steps. Analysis of the final products was as follows : w/w
- Viscosity (Brookfield; 24 °C) 705 m.P.a.s.
- the product remained stable during storage over three months at 3°C, at the end of which the appearance remained unchanged with no precipitation having occurred.
- LAPB was prepared in situ in a 60:40 w/w mixture of dipropylene glycol monomethylether:water.
- a further quantity of 80% w/w aqueous MCA (2.1g; O.Ol ⁇ mol) was added to lower the free amidoamine content, and the mixture was heated for another 16 hours at 80°C and at a pH of 9.0 to 9.5. The pH was lowered by addition of 36% w/w hydrochloric acid and the product cooled to ambient temperature.
- the overall mole ratio lauryl amidopropyl dimethylamine: MCA was 1.0:1.05.
- reaction mixture had the appearance of a mobile G-phase throughout the charging, reaction, and neutralization steps. Analysis of the final product was as follows :
- Carboxymethylated lauric hydroxyethyl imidazoline derivative was prepared in situ in an 20:80 w/w propylene glycol:water mixture.
- Lauric hydroxyethyl imidazoline (im) having 99% C content (268.Og; 1.00 mol) was added to a reaction medium comprising water (126.Og) , propylene glycol (80.4g), and 47% w/w aqueous NaOH solution (12.8g; 0.15mol) .
- reaction mixture was clear and highly mobile throughout the reaction, but became highly viscous on cooling, particularly below 55°C.
- the product was cooled to ambient temperature and the 10% solution pH adjusted to 10.0 by addition of 36% w/w hydrochloric acid.
- Viscosity (Brookfield at 25°C) l,40o m.Pa.s spindle #3, speed 10 rpm) )
- Carboxymethylated coconut hydroxyethyl imidazoline derivative was prepared in situ in an 20:80 w/w propylene glycol:water mixture.
- CHI Coconut hydroxyethyl imidazoline
- a reaction medium comprising water (198.0g), propylene glycol (91.3g), and 47% w/w aqueous NaOH solution (12.8g; 0.15 mol) .
- 80% w/w aqueous MCA solution 141.8g: 1.20 mol in total
- 47% w/w aqueous NaOH solution 109.8g: 1.29 mol in total
- the product was cooled to ambient temperature and the 10% solution pH adjusted to 8.8 by addition of 36% w/w hydrochloric acid, whereupon a precipitate of sodium chloride crystals formed.
- a further quantity of water (36g) was mixed with the product yielding a mobile, slightly turbid, amber solution free of solid precipitate.
- Viscosity (Brookfield at 25°C) 2,150 m.Pa.s spindle #3, speed 10 rpm)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL94309892A PL178957B1 (en) | 1993-11-13 | 1994-11-11 | Concentrated compositions of surfactants |
NZ275820A NZ275820A (en) | 1993-11-13 | 1994-11-11 | Surfactant composition comprising amphoteric surfactant and non-surfactant solvent mixible with water and water, the amount of surfactant being such that the composition is in a low viscosity state |
EP95900136A EP0679180A1 (en) | 1993-11-13 | 1994-11-11 | Concentrated surfactant compositions |
JP7514201A JPH08505900A (en) | 1993-11-13 | 1994-11-11 | Concentrated surfactant composition |
AU81074/94A AU678312B2 (en) | 1993-11-13 | 1994-11-11 | Concentrated surfactant compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9323449.0 | 1993-11-13 | ||
GB939323449A GB9323449D0 (en) | 1993-11-13 | 1993-11-13 | Concentrated surfactant compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995014076A1 true WO1995014076A1 (en) | 1995-05-26 |
Family
ID=10745130
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1994/003726 WO1995014076A1 (en) | 1993-11-13 | 1994-11-11 | Concentrated surfactant compositions |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0679180A1 (en) |
JP (1) | JPH08505900A (en) |
CN (1) | CN1117741A (en) |
AU (1) | AU678312B2 (en) |
CA (1) | CA2153900A1 (en) |
GB (1) | GB9323449D0 (en) |
HK (1) | HK1005778A1 (en) |
NZ (1) | NZ275820A (en) |
PL (1) | PL178957B1 (en) |
WO (1) | WO1995014076A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1413623A1 (en) * | 2002-10-23 | 2004-04-28 | Cognis Iberia, S.L. | Concentrated surface active compositions |
US7163916B2 (en) | 2004-11-17 | 2007-01-16 | Goldschmidt Gmbh | Process for the preparation of highly concentrated flowable aqueous solutions of betaines |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2763774A1 (en) * | 2009-06-08 | 2010-12-16 | The Procter & Gamble Company | Process for making a cleaning composition employing direct incorporation of concentrated surfactants |
US8809577B2 (en) * | 2012-07-20 | 2014-08-19 | E I Du Pont De Nemours And Company | Process to produce fluorinated betaines |
CN105331351B (en) * | 2015-07-15 | 2018-08-21 | 华中科技大学 | A kind of degradable water base clean fracturing fluid thickening agent in oil gas field |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2426731A1 (en) * | 1978-05-26 | 1979-12-21 | Albright & Wilson | AQUEOUS AND CONCENTRATED TENSIO-ACTIVE COMPOSITIONS |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2135641A1 (en) * | 1992-06-16 | 1993-12-23 | Allen D. Urfer | Viscosity-adjusted surfactant concentrate compositions |
-
1993
- 1993-11-13 GB GB939323449A patent/GB9323449D0/en active Pending
-
1994
- 1994-11-11 AU AU81074/94A patent/AU678312B2/en not_active Ceased
- 1994-11-11 PL PL94309892A patent/PL178957B1/en not_active IP Right Cessation
- 1994-11-11 EP EP95900136A patent/EP0679180A1/en not_active Ceased
- 1994-11-11 CA CA 2153900 patent/CA2153900A1/en not_active Abandoned
- 1994-11-11 WO PCT/EP1994/003726 patent/WO1995014076A1/en not_active Application Discontinuation
- 1994-11-11 NZ NZ275820A patent/NZ275820A/en unknown
- 1994-11-11 JP JP7514201A patent/JPH08505900A/en not_active Ceased
- 1994-11-11 CN CN 94191199 patent/CN1117741A/en active Pending
-
1998
- 1998-06-05 HK HK98104921A patent/HK1005778A1/en not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2426731A1 (en) * | 1978-05-26 | 1979-12-21 | Albright & Wilson | AQUEOUS AND CONCENTRATED TENSIO-ACTIVE COMPOSITIONS |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1413623A1 (en) * | 2002-10-23 | 2004-04-28 | Cognis Iberia, S.L. | Concentrated surface active compositions |
WO2004037963A1 (en) * | 2002-10-23 | 2004-05-06 | Cognis Ip Management Gmbh | Concentrated surface-active preparations |
US7163916B2 (en) | 2004-11-17 | 2007-01-16 | Goldschmidt Gmbh | Process for the preparation of highly concentrated flowable aqueous solutions of betaines |
US7297675B2 (en) | 2004-11-17 | 2007-11-20 | Goldschmidt Gmbh | Process for the preparation of highly concentrated flowable aqueous solutions of betaines |
Also Published As
Publication number | Publication date |
---|---|
CA2153900A1 (en) | 1995-05-26 |
GB9323449D0 (en) | 1994-01-05 |
EP0679180A1 (en) | 1995-11-02 |
NZ275820A (en) | 1997-11-24 |
PL309892A1 (en) | 1995-11-13 |
HK1005778A1 (en) | 1999-01-22 |
JPH08505900A (en) | 1996-06-25 |
AU8107494A (en) | 1995-06-06 |
PL178957B1 (en) | 2000-07-31 |
CN1117741A (en) | 1996-02-28 |
AU678312B2 (en) | 1997-05-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4861517A (en) | Method for the preparation of concentrated flowable aqueous solutions of betaines: addition of mineral acid | |
DE202008018605U1 (en) | Stable liquid cleaning compositions with a fatty acid acyl isethionate surfactant | |
US20100210500A1 (en) | Personal Wash Compositions Comprising Specific Blends of Saturated (Hydrogenated) Oil to Unsaturated Triglyceride Oils | |
WO2000076460A2 (en) | Personal care formulations | |
JPH026731B2 (en) | ||
JP2935641B2 (en) | High-purity imidazoline-based amphoteric acetate surfactants and their preparation | |
DE202008018621U1 (en) | Fatty acid acyl isethionate surfactant-containing liquid detergent compositions stabilized with a mixture of long and short chain fatty acids / fatty soaps | |
EP2627307B1 (en) | Stable liquid cleansing compositions comprising critical window of hydrogenated triglyceride oils | |
US4440665A (en) | Concentrated aqueous surfactant compositions | |
EP1546297A2 (en) | High concentration surfactant compositions and methods | |
GB2284215A (en) | Concentrated surfactant compositions | |
US5677436A (en) | Process for making alkyl polyglosides having improved aesthetic and tactile properties | |
JP4106184B2 (en) | Transparent personal care formulations containing quaternary ammonium compounds and other nitrogen-containing compounds | |
US8722604B2 (en) | Stable liquid cleansing compositions comprising critical window of partially hydrogenated triglyceride oil of defined iodine value | |
AU678312B2 (en) | Concentrated surfactant compositions | |
US4269730A (en) | Substituted imidazoline reactions with chloroacetate salts | |
WO1999027048A1 (en) | Composition containing amine oxide and betaine compounds | |
GB2023637A (en) | Concentrated Aqueous Surfactant Compositions | |
AU695480B2 (en) | Improved alkyl polyglycosides | |
JP2618311B2 (en) | Emulsion detergent composition | |
CN105326650A (en) | Stable soap base composition of liquid crystal structure | |
JP4931287B2 (en) | Liquid detergent composition | |
JP5542769B2 (en) | Method for improving low-temperature stability of aqueous solutions containing long-chain acyliminodiacetic acid type surfactant compounds | |
JP2623408B2 (en) | Emulsion detergent composition | |
JP3315828B2 (en) | Detergent composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 94191199.3 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU BR CA CN CZ FI HU JP KP KR KZ NO NZ PL RO RU SK UA US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1995900136 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 275820 Country of ref document: NZ |
|
ENP | Entry into the national phase |
Ref document number: 1995 481436 Country of ref document: US Date of ref document: 19950710 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2153900 Country of ref document: CA |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWP | Wipo information: published in national office |
Ref document number: 1995900136 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 1996 768669 Country of ref document: US Date of ref document: 19961218 Kind code of ref document: A |
|
WWR | Wipo information: refused in national office |
Ref document number: 1995900136 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1995900136 Country of ref document: EP |