WO1998035003A1

WO1998035003A1 - Detergent compound

Info

Publication number: WO1998035003A1
Application number: PCT/US1998/002366
Authority: WO
Inventors: Stephen Wayne Heinzman; Barry Thomas Ingram
Original assignee: The Procter & Gamble Company
Priority date: 1997-02-11
Filing date: 1998-02-11
Publication date: 1998-08-13
Also published as: AU6149698A; GB2321900A; BR9807832A; EP0975720A4; CA2279882A1; JP2001511209A; EP0975720A1; GB9702731D0; CN1252091A

Abstract

The present invention relates to cationic surfactants, containing at least one quaternary amine group and at least one primary, secondary or tertiary amine group. The surfactants may be used in any application where surfactancy is required. In particular they may be used in cleaning or detergent compositions or components thereof.

Description

Detergent Compound

Technical field

The present invention relates to a polyamine cationic surfactant, containing at least one quaternary amine group and at least one primary, secondary or tertiary amine group and methods for making them. The surfactants may be used in any application where surfactancy is required. In particular they may be used in cleaning or detergent compositions or components thereof.

Background to the invention

The satisfactory removal of greasy soils/stains, that is soils/ stains having a high proportion of triglycerides or fatty acids, is a challenge faced by the formulator of detergent compositions for use in laundry and dish washing methods. Surfactant components have traditionally been employed in detergent products to facilitate the removal of such greasy soils/stains. In particular, surfactant systems comprising cationic surfactants have been described for use in greasy soil/stain removal.

A wide selection of surfactants for use in detergents can be found in the literature, but the reality is that many such surfactants are chemicals which are not always suitable in detergents, because of certain properties they have (such as instability in acidic or basic environment, incompatibility with bleach, malodour problems, biodegradability problems). Thus, the challenge to the detergent manufacturer seeking improved performance has been increased by these various factors. For example, some non-biodegradable ingredients have fallen into disfavour. As a result, the manufacturer is somewhat more limited than the literature would suggest in the selection of effective, yet affordable, ingredients.

A variety of cationic surfactants are suggested to be usable in detergents. One group of cationic surfactants which is widely studied is the group consisting of quaternary ammonium or imidazolinium compounds, which are often designed for speciality use. For example, various quaternary ammonium surfactants have been suggested for use in shampoo compositions and are said to provide cosmetic benefits to hair.

US-A-4,228,042 discloses biodegradable cationic surfactants, including cationic ester surfactants for use in detergent compositions to provide greasy/oily soil removal. For example, US 3,567,729 discloses diquaternary ammonium compounds for use in detergents. For example, US 5,068,431 describes quaternary ammonium compounds, containing amphoteric amine oxide groups.

The Applicants have now found that certain polyamine cationic compounds, containing at least one cationically charged quaternary amine group and at least one primary, secondary or tertiary amine group are very good surfactants, suitable for use in cleaning or detergent compositions. These compounds are found to be very surface active under alkaline washing conditions, and they are found to give excellent cleaning performance benefits. This is believed to be due to the compounds containing both a positively charged group and a neutral, more hydrophobic group.

Furthermore, several examples of these surfactants are found to be more biodegradable and to have a very low aquatic toxicity, relative to most quaternary amine compounds.

It has been found that the stability of the polyamine cationic surfactants is not affected by changes of the pH. Furthermore, it has been found that, depending on their structure, most of the polyamine cationic compounds of the present invention and detergent compositions containing these polyamine cationic surfactants, are stable under standard storage and washing conditions.

Furthermore, it has been found that the polyamine cationic surfactants can be compatible with bleach, especially oxygen-based bleaches, and with certain bleach activators.

The polyamine cationic surfactants can be obtained via various efficient synthesis routes, and the production of these compounds can be very cost-effective.

All documents cited in the present description are, in relevant part, incoφorated herein by reference. Summary of the Invention

The present invention relates to polyamine cationic surfactants, containing at least one quaternary amine group and at least one primary, secondary or tertiary amine group. The invention also relates to methods of making the polyamine cationic surfactants. The polyamine cationic compounds of the invention can be used as a surfactant in any composition where surfactancy is required, for example in cleaning or detergent compositions or components thereof.

Detailed description of the invention

Cationic surfactant

A cationic surfactant according to the present invention comprises at least one quaternized ammonium group and at least one primary, secondary or tertiary amine group, whereby not more than one linear or branched polyoxyalkylene group is present as substituent group.

Preferred cationic surfactant of the present invention are polyamine cationic surfactants of the general formula (I):

wherein L is a linking unit, and each L is independently selected from the group consisting of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aralkylene, arylene, (poly) hydroxyaJkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L can be substituted by one or more A, B, C or D units; x is a number from 0 to 10, y is a number from 0 to 10; and wherein the units A- and D- are each independently selected from

R₂-

R, θ

B— = -N- and

M^"

R-

— C N-

R 8

wherein Ri , R2, R3, R4, R5, R _, R7 and Rg are independently selected from the group consisting of C1 -C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group and hydrogen, one of Ri , R2, R3, R4, R5, R , R7 or Rg can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or Ri and R2, Riand R2 and R3, R4 and R5 or R and R7 form together with the nitrogen atom part of a ring structure; or R3 is not present and Ri or R2 is double bonded to the nitrogen; or R7 is not present and Rg is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; or, when x and y are 0, R, or R₂ or R₃ and R_» or R5 form together with the nitrogen atoms of A and D part of a ring structure; M" is one or more counterions, and at least one A or D comprises a quaternized ammonium group in which none of Ri , R2 or R3 is hydrogen, or at least one B is present in which neither R6 nor R7 is hydrogen, and at least one A or D comprises a primary, secondary or tertiary amine group, or at least one C is present. The units B-L and C-L are linked when both are present (i.e. when x and y do not equal 0), and they can be randomly present along the chain between the end units A-L and D.

Preferably, the value of x+y is from 1 to 4. Preferably, when x+y is greater than 1, at least one of present groups A, B, C or D is a secondary or primary ammonium group.

More preferably, x=0 and y is a number from 1 to 4. Even more preferably, both x and y are 0.

If x+y does not equal 0, it is preferred that the surfactant comprises only one quaternary group A or D.

Preferably Rβ, R7 and/or Rg are each independently selected from a Ci-Cg, more preferably C1 -C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyl group or, most preferably hydrogen.

Preferably, R\ is a Cg-C 14 alkyl, (poly) hydroxyalkyl or alkoxy group or an aralkyl group, most preferably a 2-ethylhexyl group, R2 and R3 are each independently Ci-Cg, more preferably C1-C3 alkyl or hydroxyalkyl groups and preferably R4 and R5 (and Rβ, R and Rg when present) are each independently Cj-Cg, more preferably C1 -C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyl groups or, most preferably, hydrogen atoms.

In a further preferred alternative, R4 is preferably a Cβ-C\_\ alkyl, (poly) hydroxyalkyl, alkoxy group or an aralkyl group, most preferably a 2-ethylhexyl group R5 is preferably a C\-Cβ, more preferably a C1 -C3 alkyl, (poly) hydroxyalkyl group or hydrogen and R \ , R2 and R3 (and Rβ, R7 and Rg when present) are each independently preferably Ci-Cg, more preferably C1-C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyl groups or aralkyl groups.

When Ri and R2, i and R2 and R3, R4 and R5 or Rβ and R7 form together with the nitrogen atom part of a ring structure, the ring structure is preferably a benzene ring structure, moφholino ring structure or a piperazino ring structure, or a subtituted benzene or substituted moφholino or substituted piperazino ring structure. When x+y is 0 and R, or R₂ or R₃ and R₄ or R₅ form together with the nitrogen atoms of group A and D part of a ring structure, the ring structure is preferably a benzene ring structure, moφholino ring structure or a piperazino ring structure, or a substituted benzene or substituted moφholino or substituted piperazino ring structure.

L groups are independently preferably a C2-Cg, more preferably a C2-C4 linear or branched alkyl, hydroxy alkyl, alkoxy or hydroxy alkoxy group. If x+y is 0, the 1 group is preferably a C₂ alkyl group. If group L comprises more than 2 carbon atoms, the surfactant preferably comprises at least one primary or secondary A, B, C or D group.

Examples of preferred polyamine cationic surfactants of the present invention are:

R- CH-

R-

R 10 -N— L -NH 2. (V) l ^θM- R₃

R- R.

wherein Ri , R4, Rg and Rg are as described above; R2, R3 and R5 are independently selected from the group consisting of methyl, ethyl, hydroxyethyl, hydroxypropyl, polyhydroxy propyl, ethoxy, propoxy or 2,3,4,5,6-penta hydroxy hexyl, and are most preferably methyl or hydroxyethyl groups; R 10 is a methyl or hydroxyethyl group; L is as described above; R\ and/or R2 and/or R4 are most preferably a 2-ethylhexyl group.

A highly preferred cationic polyamine surfactant is of formula VI, as defined above, wherein R2 is a hydroxypropyl or hydroxyethyl group, R3 and Rio ^are methyl groups, L is C2-C3 alkyl group.

Highly preferred polyamine cationic surfactant are those of the formulas:

or

wherein Rj is as described above, preferably a C2-C14, preferably Cg-C^ linear or branched alkyl, (poly) hydroxy alkyl, alkoxy or aralkyl group; particularly preferred R\ groups are hydroxyalkyl groups, where the alkyl groups have 2 to 5 carbon atoms, especially hydroxyethyl and hydroxypropyl are preferred; particularly preferred alkyl R^ groups have up to 9 carbon atoms, most preferably R\ is a 2-ethylhexyl group; and Rn is a C2-C14 alkyl, (poly) hydroxy alkyl, alkoxy or aralkyl group or a A or D unit as described above .

The anion M" is a counterion for the cationically charged polyamine surfactant. Therefore, the number of M" anions present will depend on the cationic charge of the polyamine surfactant, which depends on the groups A, B, C and D. The number of M" anions will be at least 1. A preferred counterion is a halide anion, more preferably a sulphate anion.

Synthesis of the polyamine cationic surfactant

A variety of synthesis routes may be used for making the polyamine cationic surfactant of the present invention. Depending on which polyamine cationic surfactant reaction product is to be prepared and which starting material is available therefor, one synthesis route will be preferred over other possible routes and this choice will be well within the ambit of the skilled person given the examples below. The starting materials can be selected from a variety of (readily), commercially available compounds, depending on which polyamine cationic surfactant needs to be prepared, and again, this selection is well within the ambit of the skilled person. Preferably, the starting material is an amine or diamine compound.

Preferred synthesis routes (A-D)

A. Reaction of two amine containing compounds

A preferred synthesis route is as follows. In a preferably organic solvent one or more primary or secondary amine compound and a quaternary halide or sulphate containing amine compound are mixed, preferably in a mole ratio of 1.5: 1 to 3: 1, to make them react together. When the reaction is complete, a basic compound is added, preferably sodium hydroxide, and the polyamine cationic surfactant reaction product can be removed from the reaction mixture by conventional methods.

Examples of this synthesis route are the reactions of any of hexylamine, octylamine, decylamine, dodecylamine or 2-ethylhexylamine with (3-bromo, chloro or sulphate propyl) trimethyl ammonium bromide, chloride or sulphate, in a ratio of about 2: 1, in an organic solvent (ethanol), whereafter sodium hydroxide is added. Once the reaction is substantially completed (after reacting for up to 24 hours), the organic solvent and the possibly unreacted amine compound are removed from the reaction mixture via evaporation, and washed with (for example) diethyl ether, to yield a white solid diamine cationic surfactant, i.e. a (1- hexyl, octyl, decyl, dodecyl or 2-ethylhexyl amine) (3-trimethylamine) propane.

B. All viation of a diamine

Another preferred synthesis route is as follows.

A diamine compound and an alkylating agent are mixed in an organic solvent, preferably the diamine to alkylating agent are in a mole ratio of from 3.5: 1 to 1.1:1. When the reaction is completed the polyamine cationic surfactant reaction product can be removed from the reaction mixture by conventional methods.

Examples of this synthesis are the reactions of any of 1-bromo or chloro hexane, octane, decane, dodecane or tetradecane or 2- ethylhexylbromide with tetramethylpropanediamine in an organic solvent (ethanol). The mole ratio of the reactants is preferably about 1: 1. Once the reaction is substantially completed, the organic solvent and any unreacted amine compound are removed from the reaction mixture via evaporation. The remaining product is then washed with (for example) diethyl ether, to yield the diamine cationic surfactant, i.e. hexyl, octyl, decyl dodecyl, tetradecyl 2-ethylhexyl, tetramethyl propanediamine.

C. Preparation of an imine. reduction and alkylation

A further preferred synthesis route is as follows.

In an organic solvent an aldehyde compound and a diamine compound are mixed in a mole ratio of from 2: 1 to 1 :2, whereby an imine is formed. The imine reaction product is reduced to a secondary diamine with a reducing agent. The secondary diamine product is then selectively alkylated on the secondary amine with an alkylating agent such as formaldehyde/, formic acid. The diamine is then quaternised/ alkylated using an alkylating agent to form a diamine cationic surfactant.

Examples of this synthesis route are the reactions of any of 2-ethylhexanal, hexanal, octanal, decanal or dodecanal with N,N, dimethylene diamine in an organic solvent (toluene), in a mole ratio of about 1:1. Once the reaction is substantially completed, the solvent is removed and borohydride is added to effect the reduction step. The reduced reaction product is then neutralised with formic acid and formaldehyde. Then, methyl bromide/ chloride is added to the reaction product to yield a white solid diamine cationic surfactant, i.e. N'-hexyl, octyl, decyl, dodecyl or ethylhexyl N,N, dimethylethylene diamine.

P. Selective alkylation of diamine

Yet another preferred synthesis route is as follows:

In an organic solvent a tertiary/primary alkyl diamine and an anhydride, acid, methyl ester or acid chloride are reacted, whereby the primary amine group is acylated to produce an amide compound. The reaction product is then selectively alkylated with an alkylating agent, and the amide product is hydrolysed using a mineral acid, to produce a diamine cationic surfactant.

An example of this synthesis route is the reaction of the N,N dimethylethylene diamine with acetic anhydride in an organic solvent (toluene), followed by alkylation in an organic solvent (ethanol) with bromo- or chloro- hexane, octane, decane or dodecane to yield a quaternary amine amide. This reaction product is hydrolysed using hydrobromic acid in water, to produce a diamine cationic surfactant, i.e. a N,N,N, hexyl, octyl, decyl or dodecyl-dimethyl ethylene diamine.

Examples of small scale synthesis of preferred polyamine cationic surfactants

Example 1

hi

Into a 250ml round bottom flask fitted with reflux condenser and drying tube was placed 1-bromohexane (lO.Og, 0.061 mol) and tetramethylpropanediamine (8.68g, 0.067 mol) in 100ml ethanol. The mixture was refluxed for 72 hours. Ethanol was removed by rotary evaporation, adding additional ethanol to remove unreacted amine. The resultant sticky solid was triturated with diethyl ether, but remained a syrup. Analysis by 270 M Hz* H NMR in CDCI3 gave the following peaks: δ 0.9 (t, 4H), 1.3-1.5 (bs), 1.7 (m, 2H), 1.95 (m, 2H), 2.25 (s, 6H), 2.4 (t, 2H), 3.4-3.7 (2s, m, 14H inc. ethanol).

This synthesis was also carried out using the following materials:

1.2 replacing bromohexane with other alkyl bromides:

Bromooctane Yield 24%

Bromodecane Yield 14%

1.3 replacing tetramethylpropanediamine with tetramethylethanediamine and using the following alkyl bromides:

Alkyl Bromide Yield

Bromohexane 85 %

Bromoctane 91 %

Bromodecane 85 %

Bromotetradecane 75 %

2-Ethylexylbromide 88% Example 2

___!

Into a 250 ml round bottom flask fitted with reflux condenser and drying tube was placed octylamine (7.50g, 0.58 mol) and (3- bromopropyl)trimethylammoniumbromide (10.15g, 0.0387 mol) in 100 ml ethanol. The mixture was refluxed for 1 day. Further octylamine (2.50g, 0.0193 mol) was added and the mixture refluxed for 1 day. Sodium hydroxide (1.56g) was added and the mixture filtered to remove the resultant precipitate. Ethanol was removed by rotary evaporation, adding additional ethanol to remove unreacted amine. The resultant sticky solid was triturated with diethyl ether, to yield a white solid, (lOg, 87.60% yield). Analysis by 270 M Hz¹ H NMR in CD3OD gave the following peaks: δ 0.9(t), 1.2-1.4(bs), 1.6(m), 2.0(m), 2.5-2.7(2m), 3.2(2s), 3.4(m).

This synthesis was also carried out with the following materials:

2.2 replacing octylamine with the following alkylamines.

Butylamine Hexylamine Decylamine Dodecylamine

2-Ethylhexylamine

Detergent compositions and components thereof

The polyamine cationic surfactant of the present invention may be used in any application where surfactancy is required. For example, the polyamine cationic surfactant of the present invention can be used in detergent compositions or components thereof.

Depending on the type of detergent composition or component the polyamine cationic surfactant of the present invention can be present at a level of from 0.05% to 95% by weight of the composition or component. The detergent compositions or components thereof can contain any of the traditionally known and used detergent ingredients or components. The precise nature of these components, and levels of incoφoration thereof will depend on the physical form of the composition, and the precise nature of the washing operation for which it is to be used.

The detergent compositions or components thereof preferably contain one or more detergent components selected from additional surfactants, bleaches, bleach catalysts, bleach precursors, water-soluble and insoluble builders, chelants, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents, perfumes, brighteners and corrosion inhibitors.

The additional surfactant can be selected from anionic, nonionic, additional cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

Where present, ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.

pH of the detergent compositions

The detergent compositions preferably have a pH measured as a 1 % solution in distilled water of at least 8.5, preferably from 9.0 to 12.5, most preferably from 9.5 to 11.0.

Form of the compositions

The detergent or cleaning compositions, comprising the polyamine cationic surfactant of the present invention, can take a variety of physical forms including granular, tablet, bar and liquid forms. The compositions are particularly the so- called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load. In general, granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.

Claims

What is claimed is:

A cationic surfactant comprising at least one quaternized ammonium group and at least one primary, secondary or tertiary amine group, wherein not more than one linear or branched polyoxyalkylene group is present as substituent group.

A cationic surfactant according to Claim 1 of the general formula:

wherein L is a linking unit, and each L is independently selected from the group consisting of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aralkylene, arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L can be substituted by one or more A, B, C or D units; x is a number from 0 to 10, y is a number from 0 to 10; and wherein the units A- and D- are each independently selected from:

R₂ -

R,

Θ

B— = ^■ N - ; and M^"

R- — C — = N

R_

wherein Rj , R2, R3, R4, R5, Rβ, R7 and Rg are independently selected from the group consisting of C1-C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group and hydrogen, one of R\, R2, R3, R4, R5, R , R7 or Rg can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or R\ and R2, Riand R2 and R3, R4 and R5 or Rβ and R7 form together with the nitrogen atom part of a ring structure; or R3 is not present and R or R2 is double bonded to the nitrogen; or R7 is not present and Rβ is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; M^" is one or more counterions, and at least one A or D comprises a quaternized ammonium group in which none of Rj , R2 or R3 is hydrogen, or at least one B is present in which neither Rβ or R7 is hydrogen, and at least one A or D comprises a primary, secondary or tertiary amine group, or at least one C is present

3. A polyamine cationic surfactant according to Claim 2 wherein x=0.

4. A polyamine cationic surfactant according to Claim 2 wherein x=0 and y=0.

5. A polyamine cationic surfactant according to any of Claims 2 to 4 wherein Rl is a ₎-Ci4 alkyl group.

6. A polyamine cationic surfactant according to any of Claims 2 to 5 wherein Rl or R4 is a 2-ethylhexyl group.

7. A polyamine cationic surfactant according to Claim 5 wherein R4 and R5 are, independently from each other, Cj-Cg alkyl or (poly) hydroxyalkyl group or hydrogen atom.

8. A polyamine cationic surfactant according to any of Claims 5 or 7 wherein R4 and R5 are hydrogen.

NOT FURNISHED UPON FILING

14. A process for preparing a polyamine cationic surfactant according to any of Claims 4 to 10 comprising the steps of

(1) reaction of a diamine with an anhydride to form an acylated diamine;

(2) selective alkylation of the acylated diamine to form an acylated and alkylated diamine; and

(3) hydrolysis of the acylated alkylated diamine to form a polyamine cationic surfactant according to any of Claims 4 to 10.

15. A detergent composition or component thereof, comprising the polyamine cationic surfactant according to any of Claims 1 to 10 and comprising one of more other detergent components.

16. A detergent composition according to Claim 15 in which the detergent composition is selected from the group of anionic, nonionic surfactants, water soluble and non-soluble builders and bleaching agents.

17. A method for preparing a detergent composition according to Claim 15 or Claim 16 comprising mixing the polyamine cationic surfactant according to any of Claims 1 to 10 with one or more other detergent components.

18. Detergent compositions produced according to Claim 17.