AU682835B2

AU682835B2 - Alkylidene glycerol surfactants and detergent compositions containing them

Info

Publication number: AU682835B2
Application number: AU55623/94A
Authority: AU
Inventors: Robert John Crawford; Richard John Curtis; Abid Nadin Khan-Lodhi; Malcolm Philip Nicholls
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 1992-11-25
Filing date: 1993-11-17
Publication date: 1997-10-23
Anticipated expiration: 2013-11-17
Also published as: EP0670834B1; DE69308883D1; AU5562394A; JPH08503476A; WO1994012489A1; ES2100664T3; DE69308883T2; EP0670834A1; BR9307517A; JP2848706B2

Description

ALKYLIDENE GLYCEROL SURFACTANTS AND

DETERGENT COMPOSITIONS CONTAINING THEM

TECHNICAL FIELD

The present invention provides novel alkylidene glycerol surfactants useful in detergent compositions.

BACKGROUND AND PRIOR ART

Condensation products of aldehydes with glycerol

(alkylidene monoglycerols or monoglycerol acetals) are described in GB 414 772 (Johnson). For example, lauric aldehyde may be reacted with glycerol to give the monoglycerol acetal, described as having a five-membered dioxolane ring structure:

Such products are hydrophobic but introduction of

water-solubilising groups gives products which are useful as wetting, washing, foaming and dispersing agents. For

example, the compound shown above does not itself exhibit foaming properties, but may be converted by reaction with chlorosύlphonic acid to give a high-foaming anionic

surfactant, or ethoxylated to give a nonionic surfactant. EP 12 543A (ICI) discloses cyclic acetals and ketals of glycerol and other polyols, and their use as emollients in cosmetic, toilet and household cleaning compositions. There is disclosed the reaction product of an aldehyde RCHO with glycerol, which comprises a mixture of a five-membered ring structure A (1,3-dioxolane) and a six-membered ring structure B (1, 3-dioxane), the proportions of which can be varied in a known manner by varying the reaction conditions:

These materials may optionally be alkoxylated, acylated or alkylated.

Monoglycerol ketals are disclosed in US 3 909 460 and US 3 948 953 (McCoy/Texaco Inc). These materials, prepared by the condensation of ketones with glycerol, have the formula

where R and R' are alkyl groups containing in total 6 to 30 carbon atoms. Unlike the monoglycerol acetals, these materials can exist only in a five-membered ring form. Like the monoglycerol acetals, these materials require the

introduction of a solubilising group, for example, sulphate or polyoxyethylene, to give water-soluble surfactants.

The present inventors have now prepared acetals and ketals containing two or more glycerol residues. These materials^ which are liquids or soft solids, behave as

effective, water-soluble nonionic surfactants especially

-useful in detergent compositions for washing fabrics.

Certain combinations with other, known surfactants have been found to display synergistic oily soil detergency.

In many ways the new materials behave comparably to ethoxylated alcohol nonionic surfactants, and are potential candidates for replacing them wholly or partially in detergent compositions if a reduction in the use of ethoxylated

materials should become considered desirable on environmental grounds.

DEFINITION OF THE INVENTION

The present invention accordingly provides a compound of the formula I:

wherein R₁ represents a linear or branched alkyl or alkenyl group and R₂ represents a hydrogen atom or a linear or branched alkyl or alkenyl group, the total number of carbon atoms in R₁ and R₂ being from 7 to 17; and A represents a monoglycerol or diglycerol unit.

A second subject of the present invention is the use of a compound as defined in the previous paragraph as a surfactant or wetting agent. A third subject of the present invention is a detergent composition having a surfactant system comprising a compound as defined above.

A fourth subject of the present invention is a process for the preparation of a compound of the formula I, in which an aldehyde or ketone of the formula R₁-CO-R₂ is reacted with an oligomer of glycerol. DETAILED DESCRIPTION OF THE INVENTION

The alkylidene glycerols

The compounds of the formula I given above are believed to be novel materials. The novelty resides in the presence of more than one - specifically two or three - glycerol units in the molecule. These two classes of compounds will be referred to respectively as alkylidene diglycerols and

alkylidene triglycerols.

The diglycerols (A is a monoglycerol unit) exist as a mixture of two structural isomers, of the formulae Ila and lib:

the linear isomer Ila being the predominant species.

The triglycerols (A is a diglycerol unit) exist as a mixture of six structural isomers, as shown in the following formulae IlIa to Illf. Again, the linear isomer IlIa

predominates.

The predominant linear isomers Ila and IlIa of the alkylidene di- and triglycerols may be represented by the general formula la:

wherein n is 1 or 2.

The total number of carbon atoms in the groups R₁ and R₂ in the compounds of the invention may range from 7 to 17, preferably from 9 to 13. In principle the carbon atoms may be distributed in any proportions between the two groups.

However, the compounds studied by the present inventors fall into two classes: those in which R₂ is a hydrogen atom, and those in which R₂ is a methyl group, R₁ in both cases is a linear or branched alkyl or alkenyl group. Compounds in which R₂ is a hydrogen atom, derived from an aldehyde R₁ CHO, are referred to in the present specification as 1-alkylidene (di- or tri-)glycerols or (di- or

tri-) glycerol acetals, while compounds in which R₂ is a methyl group, derived from a methyl ketone R₁COCH₃, are referred to as 2-alkylidene (di- or tri-)glycerols or (di- or

tri-) glycerol ketals.

As may be inferred from the discussion of prior art above, the compounds in which R₂ is a hydrogen atom

(1-alkylidene di- and triglycerols, or di- or triglycerol acetals) also exist in a six-membered ring isomeric form lb:

(lb)

In practice a mixture of the two forms is normally obtained, with the five-membered ring form predominating.

The present inventors have studied the following

compounds in detail, all alkyl groups being linear: 1-decylidene diglycerol R₁ = C₉, R₂ = H

2-decylidene diglycerol R₁ = C₈, R₂ = methyl

1-dodecylidene diglycerol R₁ = C₁₁, R₂ = H

2-dodecylidene diglycerol R₁ = C₁₀, R₂ = methyl

1-decylidene triglycerol R₁ = C₉, R1 = H

1-dodecylidene triglycerol R₁ = C₁₁, R₁ = H

These materials between them are estimated to span a hydrophilic-lipophilic balance (HLB) range of about 7 to 13, making them useful in a wide range of detergent compositions, For a full discussion of HLB the reader is referred to "Surfactants in Consumer Products", ed J Falbe,

Springer-Verlag, 1987.

In physical form, alkylidene glycerols range from

liquids to solids depending on the length and nature of the alkyl or alkenyl chain, the number of glycerol units in the molecule, and the particular isomer or mixture or isomers present.

The linear 1- and 2-decylidene diglycerols are liquids of low viscosity, and are thus especially suitable for

^formulation into liquid detergent compositions, more

especially non-aqueous liquid detergent compositions. The dodecylidene diglycerols are solids, and preferred for

incorporation into particulate detergent compositions.

The HLB values of the diglycerols are estimated from phase behaviour to be 9.5-10.5, comparable to C₁₂ ethoxylated alcohol having an average degree of ethoxylation of 3-4

(hereinafter referred to for convenience as C ₁₂EO_3-4).

However, their- oily soil detergency is somewhat better.

These materials may advantageously be used in combination with cosurfactants of higher HLB (preferably ≥9 , more

preferably 9-13), such as sulphate and sulphonate-type anionic surfactants and more highly ethoxylated nonionic surfactants, for example, C_8-18EO_5-10. Synergistic oily soil detergency has been observed when the new compounds are used in

combination with primary alcohol sulphate, and with C₁₂EO₈ nonionic surfactant.

The linear decylidene and dodecylidene triglycerols are soft liquid-crystalline solids, suitable for incorporation into both aqueous liquid and particulate detergent

compositions. They are estimated to have HLB values in the range 12-13, comparable to C₁₂EO₈ nonionic surfactant. The oily soil detergency is very similar. These materials may most suitably be used in combination with cosurfactants of lower HLB (preferably ≤9 , more preferably 7-9), for example, C_8-18EO₂-₆. Synergistic oily soil detergency has been observed with C₁₂EO₃.

Preparation of the alkylidene glycerols As previously indicated, the novel alkylidene di- and triglycerols of the invention may be prepared by condensation of the appropriate aldehyde or ketone with a glycerol oligomer or mixture of oligomers.

These processes generally give more or less complex mixtures but provided that excessive amounts of

non-surface-active by-products are not present it has not in general proved necessary to isolate pure compounds.

Detergent compositions

The novel surfactants of the present invention may be incorporated in detergent compositions of all physical types, for example, powders, liquids, gels and solid bars.

These compositions, whatever their physical form, will generally contain detergent-active compounds and detergency builders, and may optionally contain bleaching components and other active ingredients to enhance performance and

properties.

Detergent-active compounds

The detergent compositions of the invention will

contain a surfactant system comprising one or more

detergent-active compounds (surfactants), the surfactant system consisting at least in part of an alkylidene di- or triglycerol in accordance with the present invention. As indicated, one or more cosurfactants may also be present. These may be chosen from soap and non-soap anionic, caifionic, nonionic, amphoteric and zwitterionic

detergent-active compounds, and mixtures thereof. Many suitable detergent-active compounds are available and are fully described in the literature, for example, in

"Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.

The preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and nonionic -compounds.

Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates,

particularly linear alkylbenzene sulphonates having an alkyl chain length of C₈-C₁₅; primary and secondary alkyl

sulphates, particularly C₁₂-C₁₅ Primary alkyl sulphates;

alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates. -Sodium salts are generally preferred. Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C_8-C₂₀ aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C_10-C₁₅ primary and secondary

aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.

Non-ethoxylated nonionic surfactants include

alkylpolyglycosides, glycerol monoethers, and

polyhydroxyamides (glucamide). The total amount of surfactant present will depend on the intended end use and may be as low as 0.5 wt%, for example, in a machine dishwashing composition, or as high as 60 wt%, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wt% is generally appropriate. Detergency builders

The detergent compositions of the invention will

generally also contain one or detergency builders. The total amount of detergency builder in the compositions will suitably range from 5 to 80 wt%, preferably from 10 to 60 wt% in powders, from 5 to 25 wt% in aqueous liquids and from 10 to 40 wt% in non-aqueous liquids.

Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950

(Unilever); crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201 (Henkel), amorphous aluminosilicates as disclosed in GB 1 473 202

(Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble); and layered silicates as disclosed in EP 164 514B (Hoechst). Inorganic phosphate builders, for example, sodium orthophosphate, pyrophosphate and tripolyphosphate, may also be present, but on environmental grounds those are no longer preferred. Zeolite builders may suitably be present in amounts of from 5 to 60 wt%, preferably from 10 to 50 wt%. Amounts of from 10 to 45 wt% are being especially suitable for

particulate (machine) fabric washing compositions. The zeolite used in most commercial particulate detergent

compositions is zeolite A. Advantageously, however, maximum aluminium zeolite P (zeolite MAP) described and claimed in EP 384 070A (Unilever) may be used. Zeolite MAP is an alkali metal aluminosilicate of the P type having a silicon to aluminium ratio not exceeding 1.33, preferably not exceeding 1.15, and more preferably not exceeding 1.07.

Organic builders that may be present include

polycarboxylate polymers such as polyacrylates,

acrylic/maleic copolymers, and acrylic phosphinates;

monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.

Especially preferred organic builders are citrates, suitably used in amounts of from 5 to 30 wt%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.

Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.

Bleach components

Detergent compositions according to the invention may also suitably contain a bleach system. Machine dishwashing compositions may suitably contain a chlorine bleach system, while fabric washing compositions may more desirably contain peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.

Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates,

perphosphates, persilicates and persulphates. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.

Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture.

Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in

GB 2 123 044B (Kao). The peroxy bleach compound is suitably present in an amount of from 5 to 35 wt% , preferably from 10 to 25 wt%.

The peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve

bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of from 1 to 8 wt%, preferably from 2 to 5 wt%. Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors. An especially preferred bleach precursor suitable for use in the present invention is N,N,N' ,N' -tetracetyl ethylenediamine (TAED).

A bleach stabiliser (heavy metal sequestrant) may also be present. Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP.

An especially preferred bleach system comprises a peroxy bleach compound (preferably sodium percarbonate or sodium perborate monohydrate) optionally together with a bleach activator), and a transition metal bleach catalyst as

described and claimed in EP 458 397A, EP 458 398A and

EP 509 787A (Unilever).

Other ingredients

Detergent compositions of the invention may contain alkali metal, preferably sodium, carbonate, in order to increase detergency and ease processing. Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%. However, compositions containing little or no sodium carbonate are also within the scope of the invention. In particulate detergent compositions, powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate. A preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt%.

Other materials that may be present in detergent

compositions of the invention include sodium silicate;

antiredeposition agents such as cellulosic polymers;

fluorescers; inorganic salts such as sodium sulphate; lather -control agents or lather boosters as appropriate; proteolytic and lipolytic enzymes; dyes; coloured speckles; perfumes; foam controllers; and fabric softening compounds. This list is not intended to be exhaustive.

Liquid detergent compositions

As previously indicated, alkylidene di- and triglycerols in accordance with the present invention may advantageously be incorporated into both aqueous and non-aqueous liquid

detergent compositions. Aqueous liquids in accordance with the invention may be isotropic. Alternatively they may be structured liquids comprising a dispersion of lamellar droplets in an aqueous continuous phase, optionally containing suspended particulate solid. Structured liquids of this type without suspended solid are disclosed, for example, in US 4 244 840, while structured liquids containing suspended solids are disclosed in US 4 244 840 and also in EP 38 101A, EP 160 342A and

EP 140 452A. The liquids may contain a deflocculating polymer as described and claimed in EP 346 995A (Unilever), suitably in an amount of from 0.01 to 5 wt%. Non-aqueous liquids in accordance with the invention contain not more than 5 wt%, and preferably less than 3 wt%, water. They may take the form of a particulate solid phase dispersed in a non-aqueous liquid phase, the latter comprising one or more nonionic surfactants, suitably in an amount of from 1 to 90 wt%, preferably from 5 to 75 wt% and more

preferably from 20 to 60 wt%. Advantageously the non-aqueous liquids may contain a hydrophobically modified dispersant, for example, a hydrophobic silica, to improve physical stability. A deflocculant, for example, an acid as described and claimed in EP 266 199A (Unilever), may also advantageously be present.

EXAMPLES

The invention is further illustrated by the following non-limiting Examples, in which parts and percentages are by weight unless otherwise stated. Numbered Examples are within the invention, while those identified by a letter are

comparative.

EXAMPLES 1 to 4

Synthesis and characterisation of alkylidene di- and

triglycerols

Example 1: preparation of 1-decylidene diglycerol

This example describes the preparation of a compound of the formula I in which R₁ = linear C₉H₁₉, R₂ = H, A =

monoglycerol.

1, 1-Dimethoxydecane (22.0g, 0.10mol), diglycerol (86.0g, 0.52mol) and p-toluene sulphonic acid (0.25g) in dimethyl formamide (100 cm³) were heated at 100°C for 7 hours. The reaction mixture was allowed to cool and water (400 cm ³) was added and the mixture extracted with ether (2x300 cm³). The combined ether extracts were washed with water (2x250 cm 3 ) and brine (250 cm ³_) and dried over anhydrous sodium sulphate. The solvent was removed at reduced pressure to give the crude product. Short path distillation using a Kugelrohr apparatus afforded pure 1-decylidene diglycerol (14.7g, 48%).

The compound was characterised by nuclear magnetic resonance (NMR) spectroscopy: delta_H (360 MHz, CDCl₃, TMS) 0.89 (3H, t, CH₃-), 1.3-1.4 (14H, m, -(CH₂)₇-), 1.65 (2H, m, C₈H₁₇-CH₂-), 3.5-4.4 (10H, m, -O-CH₂-CH(O)-CH₂-O-), 4.88,4.98 (1H, t, C₉H₁₉-CH-).

A similar method was used to prepare and characterise 1-dodecylidene diglycerol. Example 2: preparation of 2-decylidene diglycerol

This example describes the preparation of a compound of the formula I in which R₁ = linear C₈H₁₇, R₂ = methyl, A = monoglycerol. 2-Decanone (0.136 mol), diglycerol (340.0g, 2.05mol, 15 equiv) and p-toluene sulphonic acid (0.5g) in dimethyl formamide (340 cm³) were stirred together at 100°C for 3-6 hours. The reaction mixture was allowed to cool, water (250 cm³) was added and the mixture extracted with ether. The ether extracts were washed with water and brine and dried over anhydrous sodium sulphate. The solvent was removed on a rotary evaporator to give crude product. Short path

distillation using a Kugelrohr apparatus afforded pure

2-decylidene diglycerol (12.52g, 30%) The compound was characterised by nuclear magnetic resonance (NMR) spectroscopy: delta_H (360 MHz, CDCl₃, TMS) 0.88 (3H, t J = 6.9 Hz, CH₃ ), 1.3 (12H, m, -(CH₂)₆-),

1.31,1.37 (3H, s, O-C(CH₃)C₈H₁₇-O), 1.65 (2H, m, C₇H₁₅-CH₂-), 2.2-3.0 (2H,br m, -OH), 3.6-4.4 (10H, m, -O-CH₂-CH(O) -CH₂-O-).

Example 3: preparation of 2-dodecylidene diglycerol

This example describes the preparation of a compound of the formula I in which R₁ = linear C₁₀H₂₁, R₂ = methyl, A = monoglycerol. 2-Dodecanone (0.136 mol), diglycerol (340. Og, 2.05mol,

15 equiv) and p-toluene sulphonic acid (0.5g) in dimethyl formamide. (340 cm ) were stirred together at 100 C for 3-6 hours. The reaction mixture was allowed to cool, water (250 -cm³) was added and the mixture extracted with ether. The ether extracts were washed with water and brine and dried over anhydrous sodium sulphate. The solvent was removed on a rotary evaporator to give crude product. Short path

distillation using a Kugelrohr afforded pure 2-dodecylidene diglycerol (21.3g, 47%) b.p. 225°C / 0.04mbar. The compound was characterised by nuclear magnetic resonance (NMR) spectroscopy: delta_H (360 MHz, CDCl₃, TMS) 0.88 (3H,_t J = 6.9 HZ, CH₃), 1.3 (17(?)H, m, -(CH₂)₈-),

1.3_1,1.36 (3H, s, O-C(CH₃)C₁₀H₂₁-O), 1.65 (2H, m, C₉H₁₉-CH₂-), 2.2-3.0 (2H, br m, -OH), 3.5-4.4 (10H, m,

-O-CH₂-CH(O)-CH₂-O-).

Example 4: preparation of 1-decylidene triglycerol

This example describes the preparation of a compound of the formula I in which R₁ = linear C₈H₁₇, R₂ = H, A =

diglycerol. 1, 1-Dimethoxydodecane (11.5g, 0.05mol), triglycerol

(240g, 1.0mol) and p-toluene sulphonic acid (0.5g) in dimethyl formamide (250 cm³) was heated at 100°C for 5 hours. The reaction mixture was allowed to cool and water (400 cm³) was added and the mixture extracted with ether (2x300 cm³). The combined ether extracts were washed with water (2x250 cm³) and brine (250 cm³ ) and dried over anhydrous sodium sulphate. The solvent was removed at reduced pressure to give the crude product. Short path distillation using a Kugelrohr apparatus was used to remove low boiling impurities to leave near-pure 1-dodecylidene triglycerol ( 14.2g, 70%).

The compound was characterised by nuclear magnetic resonance (NMR) spectroscopy: delta., (360 MHz, CDCl , TMS) 0.88 (3H, t, CH3-), 1.3-1.4 (18H, m, -(CH₂)₉-), 1.64 (2H, m, C₁₀H₂₁-CH₂-), 3.5-4.4 (15H, m, -O-CH₂-CH(O)-CH₂-O-), 4.88,4.97 (1H, t, C₁₁H₂₃-CH-).

A similar method was used to prepare and characterise 1-dodecylidene triglycerol.

EXAMPLES 5 TO 8 - DETERGENCY

Oily soil detergencies were compared in triolein removal experiments using the Tergotometer.

³H-radiolabelled triolein was used to assess soil removal. Knitted polyester test cloths carrying this soil

(level about 1.9%) were washed in the Tergotometer UR 7227 for

20 minutes, the agitation being 70 rpm, the wash liquor volume being 500_ml, and the wash temperature being 40ºC. The surfactants were used at a concentration of 1 g/litre in

-distilled water in the presence of sodium metaborate buffer

(0.05M). Subsequent to the wash, 4 x 1 ml samples of wash liquor were removed from each tergotometer pot and the

activity determined using a liquid scintillation counter.

Percentage detergency was calculated from the

relationship:

% detergency = A_w

--------------------------------- A_s 100 where A_w is the total activity in the wash liquor and A_s is the level of activity originally applied to the cloth.

The decylidene and dodecylidene diglycerols all showed synergistic detergency behaviour when used in combination with the high-HLB cosurfactants, primary alcohol sulphate (cocoPAS) and C₁₂EO₈ ethoxylated alcohol. Example 5

2-decylidene diglycerol (Example 2 ) with primary alcohol sulphate (cocoPAS)

Surfactant mixture (%) Triolein removal (%)

2-decvlidene cocoPAS

diglycerol

100 0 30

80 20 68

60 40 52

40 60 48

20 80 46

0 100 44

Example 6

2-dodecylidene diglycerol (Example 3) with cocoPAS

Surfactant mixture (%) Triolein removal (%)

2-dodecylidene cocoPAS

diglycerol

100 0 8

80 20 60

60 40 68

40 60 66

20 80 58

0 100 44 Example 7

2-decylidene diglycerol (Example 2) with C₁₂EO₈ nonionic surfactant

Surfactant mixture (%) Triolein removal (%)

2-decylidene

C₁₂EO₈

diglycerol nonionic

100 0 6

80 20 54

60 40 74

40 60 73

20 80 69

0 100 58

Example 8

2-dodecylidene diglycerol (Example 3) with C₁₂EO₈ nonionic surfactant

Surfactant mixture (%) Triolein removal (%)

2 -dodecylidene C_{1 2}EO₈

diglycerol nonionic

100 0 35

80 20 69

60 40 68

40 60 69

20 80 64

0 100 58 EXAMPLES 9 TO 12- DETERGENCY

In these Examples, detergencies were measured by a method similar to that used in Examples 5 to 8, but the tergotometer wash liquors contained the following ingredients in 24

(French) hard water: g/litre

surfactant (total) 1.00

zeolite 2.42

sodium carbonate 1.82

acrylic/maleic copolymer 0.592

Example 9

1-decylidene diglycerol (Example 1) with cocoPAS

Surfactant mixture (%) Triolein removal (%)

1-decylidene cocoPAS

diglycerol

100 0 2.5

80 20 58.6

60 40 58.2

40 60 52.8

20 80 44.7

0 100 40.1 Example 10

1-decylidene diglycerol (Example 1) with nonionic surfactant

Surfactant mixture (%) Triolein removal (%)

1-decylidene C_10-12EO₇

diglycerol nonionic

100 0 2.1

80 20 51.5

60 40 62.7

40 60 61.3

20 80 64.9

0 100 60.7

Example 11

1-dodecylidene diglycerol (Example 1) with nonionic surfactant

Surfactant mixture (%) Triolein removal (%) 1-dodecylidene C_{10- 2}EO₇

diglycerol nonionic

100 0 1.5

80 20 4.9

60 40 62.0

40 60 65.9

20 80 65.0

0 100 60 . 7 Example 12

1-dodecylidene triglycerol (Example 4) with nonionic

surfactants

With 7EO nonionic surfactant:

Surfactant mixture (%) Triolein removal (%)

1-dodecylidene C₁₀_₁₂EO₇

triglycerol nonionic

100 0 60.3

80 20 57.7

60 40 58.8

40 60 62.2

20 80 22.6

0 100 60.7

With 3EO nonionic surfactant:

Surfactant mixture (%) Triolein removal (%)

1-dodecylidene C_10-12 EO₃

triglycerol nonionic

100 0 61.1

80 20 65.1

60 40 60.8

40 60 6.5

20 80 3.2

0 100 0.7

These results show that 1-dodecylidene triglycerol behaved as a high-HLB surfactant. Little benefit was obtained from mixing it with another high-HLB surfactant, 7EO ethoxylated nonionic, the two surfactants exhibiting very similar performance. However, when it was mixed with a low-HLB surfactant, 3E0 ethoxylated alcohol, enhanced

detergency was observed.

EXAMPLES 13 TO 16 - DETERGENT COMPOSITIONS

Examples 13 and 14 - detergent powders

-Detergent powders incorporating the compounds of the invention may be prepared to the following formulations (weight %):

13 14 Decylidene or dodecylidene

diglycerol 17 -

Decylidene or dodecylidene

triglycerol — 8.5 C _12-15 EO (ay)₇.ethoxylate 8.5 zeolite 32 32 sodium carbonate 12 12 alkaline sodium silicate 0.5 0.5 fatty acid soap 2 2 sodium carboxymethylcellulose 0.6 0.6 sodium perborate monohydrate 15 15

TAED 6.5 6.5 bleach stabiliser (EDTMP) 0.4 0.4 silicone suds suppressor 0.4 0.4 enzymes 1.0 1.0 fluorescer 0.2 0.2 perfume 0.6 0.6 moisture and salts to 100% Example 15: non-acrueous liguid detergent weight %

Decyl- or dodecylidene diglycerol 25.3

C_10-15 EO(av)₇ ethoxylate 25.3

sodium carbonate 17

sodium perborate monohydrate 10.5

alkylbenzene sulphonic acid 6

calcium carbonate 6

silica (dispersant) 4

silicone suds suppressor 2.75

antiashing polymer 1.5

antiredeposition polymer 1.5

fluorescer 0.15

Examples 16 and 17: aqueous liquid detergents weight %

16 17 decyl- or dodecylidene

triglycerol 25 - decyl- or dodecylidene

diglycerol - 12.5

C_10-15EO(av)₇ ethoxylate - 12.5 fatty acid 4.5 4.5 potassium hydroxide 10 10 zeolite 15 15 citric acid 8 8 glycerol 2 2 borax 1.5 1.5 polymer 1.0 1.0 silicone oil 0.3 0.3 enzymes 0.5 0.5 perfume 0.5 0.5 water to 100%

Claims

A compound of the formula I:

wherein R₁ represents a linear or branched alkyl or alkenyl group and R₂ represents a hydrogen atom or a linear or branched alkyl or alkenyl group, the total number of carbon atoms in R₁ and R₂ being from 7 to 17; and A represents a monoglycerol or diglycerol unit.

A compound as claimed in claim 1, having the formula la:

wherein n is 1 or 2 . 3 A compound as claimed in claim 1 , wherein R₁ represents a C₉ or C₁₁ alkyl group, and R represents a hydrogen atom.

4 A compound as claimed in claim 1, wherein R₁ represents a C₈ or C₁₀ alkyl group, and R₂ represents a methyl group.

5 Use of a compound as claimed in claim 1 as a surfactant or wetting agent.

6 A detergent composition containing a surfactant system comprising one or more surface-active compounds, characterised in that the surfactant system comprises a compound as claimed in claim 1.

7 A detergent composition as claimed in claim 6, comprising as surfactant system a compound of the formula I wherein A is a monoglycerol unit in combination with a cosurfactant having an HLB value of at least 9.

8 A detergent composition as claimed in claim 7, wherein the cosurfactant has an HLB value of from 9 to 13.

9 A detergent composition as claimed in claim 7, wherein the cosurfactant is selected from sulphate and sulphonate anionic surfactants and ethoxylated nonionic surfactants.

10 A detergent composition as claimed in claim 7, wherein the cosurfactant is a primary alcohol sulphate. 11 A detergent composition as claimed in claim 7, wherein the cosurfactant is a C_{8 -18} alcohol ethoxylated with an average of 5 to 10 moles of ethylene oxide per mole of alcohol.

12 A detergent composition as claimed in claim 6, comprising as surfactant system a compound of the formula I wherein A represents a diglycerol unit, in combination with a

cosurfactant having an HLB value not exceeding 9.

13 A detergent composition as claimed in claim 12, wherein the cosurfactant has an HLB value within the range of from 7 to 9.

14 A detergent composition as claimed in claim 12, wherein the cosurfactant is an ethoxylated nonionic surfactant.

15 A detergent composition as claimed in claim 12, wherein the cosurfactant is a C_8-18 alcohol ethoxylated with an average of 2 to 6 moles of ethylene oxide per mole of alcohol

16 A detergent composition as claimed in claim 6, which is in liquid form.

17 A detergent composition as claimed in claim 6, which is in non-aqueous liquid form.

18 A process for the preparation of a compound as claimed in claim 1, which comprises reacting an aldehyde or ketone of the formula R₁ -CO-R- with an oligomer of glycerol.