DE2226934A1 - QUATERNAERE AMMONIUM COMPOUNDS AND THEIR USE FOR SURFACE TREATMENT - Google Patents

Description

LAWYERS

DR. IUR. DiPL-CHEM-WALTER AT

ALFRED IiO = PPENER

DR. JUß. DiPL-CHiM. H.-J. WOLFF Q 1

DR. JUR. HANS CHR. BEIL * '·

FRANKFURTAM MAIN-HOCHST

AOiIONSIRAiSE SI

Our no. 17 939

The Procter & Gamble Company Cincinnati, Ohio, V.St.A.

Quaternary ammonium compounds and their use for surface treatment .

The present invention relates to new quaternary ammonium imides which are surface active agents and can be in zwitterionic or cationic form.

Quaternary ammonium compounds that have at least one long-chain (about Cq upwards) hydrophobic residue in the molecule have been known for a long time. They are available as cationic surfactants (so-called "invert soaps"),

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useful as fabric softeners and as bactericides. at When used as a surfactant, the long chain group usually has about 12 to 20 carbon atoms on, while long-chain compounds for use as fabric softeners, for example those with about 16-22 or more carbon atoms, are preferred, especially Compounds with 2 long-chain groups. Typical examples include octadecyldimethylbenzylammonium chloride, Octadecyltrimethylammonium chloride, dis te aryl dimethyl ammonium chloride, the corresponding bromides and many others of similar structure.

These compounds, especially distearyldimethylammonium chloride, have been used commercially in fabric softener blends intended for addition to the latter Rinse water are provided after a conventional washing process, and attempts have been made to use them in To use detergent and cleaning agent mixtures, which serve as combined detergents and fabric softeners should.

Since these substances are cationic, they usually react with anionic detergents to form insoluble substances and therefore their use in the presence of anionic detergents normally comes practically out of consideration. They also have a strong affinity for fabrics, especially cotton and wool, a fact that plays an important role in their effectiveness as fabric softeners and bactericides, but also the consequence is that they are generally completely washed out of the fabric in a subsequent wash will. They therefore tend to accumulate on repeatedly laundered fabrics, while reducing the rewetting properties which can affect the tissues and cause them to become discolored, rigid and even undesirable

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Can cause odors. Such tissues, although soft to the touch, often have an unpleasant "greasy" Handle when they have been subjected to multiple treatments. A similar effect is observed on hard surfaces. Thus, when using cationic surfactants as sterilizing agents in dish or glass washing are used, a hydrophobic layer remains adsorbed on the surface, which when rewetted gives a "greasy" appearance.

Other quaternary ammonium compounds are the. known zwitterionic surface-active compounds, for example long-chain carboxylic acid betaines, sulfobetaines, SuIfato- and sulfitobetaines. These connections are valuable wetting agents and detergents. Since they are internal salts, they do not react with those in hard water present metal ions, especially calcium ions, and are thus almost not influenced by the hardness of the water. For the same reason they are compatible with anionic, cationic and nonionic detergents. Her Affinity for strongly hydrophobic fibers, such as polyamide or polyester fibers, and their wetting effect on them makes them special for removing certain types of dirt, especially greasy dirt, from these materials valuable. You are also at the cleaning of cotton fabrics that are made with clay or. Containing dust particles Dirt contaminated are remarkably effective. However, they are not strongly noun towards tissues and are not very effective fabric softening agents. These known betaines and betaine-like compounds exist within a wide pH range in zwitterionic form ·. Under relatively strongly acidic conditions they become cationic, however, the acidity required is outside the range required for the V / ascheai of tissues or for the Body wash comes into consideration. . -

According to the invention, there is a new class of detergents applied which are cationic under weakly acidic conditions and zwitterionic under weakly alkaline conditions where the acidity or alkalinity is related to its ρΚα value as defined below. If so with the usual pH-value of a rinsing process in an aqueous one Solution (which does not necessarily have to be the rinsing liquid after a wash), they are mostly present in cationic form and as a fabric softener, which are noun for tissue, effective; under the usual alkaline conditions of a subsequent However, they are converted into zwitterionic form and are then compared to fabrics not noun. In this form, they are compatible with the detergent and cleaning agent mixture.

Both on textile fibers and on other surfaces, for example hard surfaces, the adsorbed cationic and / or zwitterionic layer a surface that shows the tendency towards important classes of dirt (or dust or clay-containing dirt) and their separation from the surface and their dispersion in one to favor subsequent alkaline washing if the adsorbed layer does not become noun. These substances can thus act as soil releasing agents that are removed with each washing process, and they can be used in a rinsing process or a similar treatment before the time at which the surface of the contamination re-exposed, re-applied. You can use the treated surfaces also impart antistatic and bactericidal properties and some of these substances act as an inhibitor the transfer of dyes from one article or part of an article to another in washing solutions and the like.

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According to the present invention, quaternary ammonium imides are used with the general formula

-R

CO N "00 CH ₂ N ⁺

■ 4

or their cationic adducts with the general formula

CO KH CO CH

created in what

X an anion,

R _{1 is} an alkyl group with 1 Ms of 25 carbon atoms or a phenyl or a benzyl group or an alkylbenzene or alkylphenyl group with 8 to 18 carbon atoms in the alkyl radical,

R _{2 is} an alkyl group with 1 to 26 carbon atoms or a benzyl or phenyl radical,

Each of the radicals R, and R ^ is an alkyl group with 1 to 4 carbon atoms or a phenyl or benzyl radical or R ₂ , R, and R ^ together represent a pyridine ring and one or both radicals R ₁ and R ₂ contain at least 10 carbon atoms,

symbolize.

Particularly advantageous compounds are those of the general formula given above, in which R _{1 is} an alkylbenzyl group having 12 to 14 carbon atoms in the alkyl group or an alkyl group having 13 to 21 carbon atoms and R 1 and 2

In each case a methyl or ethyl group or

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a phenyl or benzyl group or together represent a pyridine ring, particularly preferred compounds being those in which Hp ₁ R- * and R. each represent a methyl group. Other suitable compounds are those of the general formula in which each of the radicals R ^, R, and R ^ is a short-chain group, either alkyl having 1 to 6 carbon atoms or phenyl or benzyl, and Rp is a long-chain alkyl group having 10 to 26, preferably 14 to Represents 22 carbon atoms. In these compounds, R 1 is preferably methyl or ethyl, in particular methyl. Further suitable compounds are those in which both R 1 and R p, which need not be the same, are long-chain groups of the type defined above.

The compounds of the invention can be prepared by any suitable method, but one suitable method is by reaction; of an amide R. CO NH ₂ with chloroacetyl chloride and then the reaction of the product with a tertiary amine

N - E ₃ ,
in which the radicals R have the meaning given above.

In order for the compounds to be surfactants, they must, as indicated above, at least one long chain Have hydrophobic group and can carry two such groups. Usually it is used in the preparation of the connections preferably of a long-chain amide, for example a fatty acylamide with about 10 to 26 carbon atoms, preferably 14 to 22 carbon atoms to assume that derived from fats or other sources of high molecular weight fatty acids, or an alkylbenzyl or alkylphenyl amide with about 8 to 18, preferably about 12 to 14 carbon atoms in the alkyl chain.

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In particular, the amide of. a typical detergent alkoxide derived via the corresponding alkylbenzyl chloride be.

The tertiary amine can be used as a source for a long chain hydrophobic group, in which case it may contain a long chain alkyl group as described above. the remaining groups are usually short-chain groups such as methyl, ethyl, or they can be benzyl or phenyl groups be.

Alternatively, Rp, R, and R ^ together can be heterocyclic Ring, such as a pyridine ring. The preferred tertiary amine is trimethylamine

In aqueous solution and outside of aqueous solution, the imides according to the invention can either be in cationic Form at relatively low pH, or in zwitterionic Form exist at relatively high pH and they have a ρΚα value in the range from 7 to 10, usually 8 to 8.5 ». The ρΚα value is the pH value at which the compounds 50 mol% in zwitterionic and 50 mol% in in cationic form. Thus they are predominantly cationic at low pH and zwitterionic at high pH, but at a pH value close to the ρΚα value, both can Forms to a considerable extent.

The invention also provides new compositions created for surface treatment, which one or more common components of such mixtures and a quaternary Ammonium imide, as defined above, contain, the imide having a ρΚα value in the range from 7 to 10.

These compositions are more useful as fabric softeners do not pile up on textiles and

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■ 42658.

Do not impair the wettability of textiles that have been repeatedly treated with it, and do not discolour or "grease" the textiles. Furthermore, they act as a soil-repellent and / or soil releasing agents so that contaminated surfaces are more easily cleaned of textiles and other materials in a subsequent wash, for example when the washing-in is carried out a relatively low temperature (lower than 60 ⁰ C), in particular in less ideal Wasclibedingungen, and / or when a lower than optimal concentration of a common household laundry detergent and cleaning agent mixture is used. They are particularly valuable in helping to remove greasy and greasy particulate soils, as well as clay or dusty soils, from textiles and hard surfaces.

It is often convenient to use the compositions according to the invention at certain stages during a washing process, for example in the rinsing section, and they can be used in such a way as that for the "rinsing additives" is known. It should be noted that the first so-called "rinsing" of a new article can be carried out, before it is washed or worn for the first time for dirt-repellent properties and other benefits. Thus, the present invention also provides a fabric treatment rinse aid mixture which has a compound according to the invention together with a pH buffer such type and amount that the pH of the solution of the mixture, especially one having such a concentration has that 0.1% by weight of the compound in cationic Form is lower or not higher than 2 units above the ρΚα value of the surface-active Means lies. The solution of the mixture can be an aqueous one, for example in tap water, or it can be Be a rinse solution after a customary, generally alkaline wash.

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The mixtures are particularly effective when they are buffered in such a way that the pH of the solution is close to the ρΚα value, for example within 2 pH units above or below it, in particular within about 1 unit. Suitable buffer compounds are known per se and include water-soluble phosphates, borates, carbonates, citrates, tartrates and the like, and the corresponding acids. The proportions of the components in such mixtures depend on the manner in which the mixtures are to be used and on the nature of the components selected. Conveniently, the amount of the cationic form of the surfactant present can be in the range from about 0.01 to 0.5 % based on the dry weight of the tissue to be treated, for example about 0.1%.

On a different basis, contain effective · rinse additives about 1 to 20% by weight, for example about 5% by weight, of the cationic form of the surfactant and are used at a concentration of about 0.2 to 0.5% by weight in the treatment solution, but they are Numbers are not to be understood as limiting.

The compositions according to the invention can alternatively be used as alkaline washing and cleaning agent mixtures. with the advantage of the valuable detergent properties the zwitterionic form of the imides according to the invention is obtained. Such mixtures can be the common alkaline detergent builder salts and complexing agents and also other non-cationic ones surfactants. After dilution with tap water or the like. in a rinsing section to reduce the pH value tes to a value close to or below the ρΚα value the proportion of the imide according to the invention that remains, to a considerable extent cationic and

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shen surface noun, being those described above Benefits are obtained. Such detergent mixtures containing builders usually contain detergent and cleaning agent mixtures Detergent builder salts and total organic surfactant in a weight ratio in the range from about 1: 4 to 30: 1.

Another embodiment of the application of the compositions as fabric softeners consists in the approach of the same as soaking compositions. The fabrics to be washed are subjected to a previous soaking or wetting in an aqueous solution containing the cationic form of a compound according to the invention. A conventional detergent and cleaning agent mixture can then be added to the same solution and washing and Flushing is carried out in the usual way. Alternatively, the excess solution can be separated from the Gev / just, for example by spin drying, and then the fabrics can be washed and rinsed as usual.

These soaking compositions need only contain the compound of the invention, but usually contain also a dilution or carrier medium. It is often useful to use other zwitterionic or nonionic incorporating surfactants to improve the solubility of the quaternary ammonium imide.

The compositions described above, whether or not alkaline, can include compatible components common compositions of the class to which they belong. So can the alkaline detergent mixes Builders as mentioned above contain, for example water-soluble, usually alkali metal, especially sodium or potassium phosphates and polyphosphates, carbonates, silicates, etc., and chelating agents,

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such as mtrilotriacetate, polycarboxylates, such as those used in British Patent No. 1,054-,755 are, and citrates, gluconates, etc. Neutral salts, such as alkali metal chlorides and sulfates, can also be present, also bleaching agents such as sodium perborate, percarbonates and perphosphates. Minor components that may also be present include: foam regulating agents Agents, enzymes, activators or stabilizers for enzymes, enzymes and / or for the bleaching agents, dust inhibitors, etc. Mixtures of any kind can contain chelating agents that are effective at the appropriate pH, optical brighteners, perfumes, coloring materials and, if the mixtures are liquid, emulsifiers, hydrotropes, Solvents, and the like. Some of these components may have more than one function and, for example, both be effective as a buffering agent as well as a chelating agent.

In the alkaline detergent and cleaning agent mixtures are the quaternary ammonium imides in non-cationic Form compatible with other surfactants from any class'.

In the mixtures in which the imide is cationic Form is present, preferably lacking anionic detergents. Suitable anionic detergents, if compatible, include the sulfonic and sulfuric acid derivatives, such as alkylarylsulfonates, Alkyl sulfates, alkyl ether sulfates and many others known in the relevant art. Suitable nonionic detergents include polyethoxy alcohols, Alkylphenols, fatty acids, amines and the like, polyethoxy / polypropylene oxide konderis ate, Polyäthoxys orbitanes ter and many others. Suitable zwitterionic products include: quaternary ammonium carboxylates (betaines), sulfonates (Sulfobetaines) and the like, some of which are mentioned above. Semi-polar nonionic surfactants such as tertiary Amine oxides or phosphine oxides can also be present.

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The following examples illustrate the inventor

manure:

Example "1 j Commercially available linear dode-

cylbenzene is converted into the dodecylbenzyl-

chloride and then via the corresponding nitrile to dodecylphenylacetamide converted. The ortho- and para-isomers are present in a ratio of about 1: 4.

5.4 g of dodecylphenylacetamide and 15 ml of chloroacetyl chloride are heated under reflux for 2 hours. Excess chloroacetyl chloride is reduced by evaporation under reduced pressure The pressure is removed and the residue is dissolved in 50 ml of acetone. A large excess of gaseous trimethylamine is passed through in this solution for 1 hour and the mixture is then left to stand for 16 hours, whereupon the brown, crystalline Product (1) is filtered off. The reaction can be illustrated as follows:

! 2 ¹ VX-J

Γ \

3H ₂ CO NH ₂

+ Cl CO

Cl

° 12 ^H 25 vJ

^C 12 ^H 25 "\ -

^{C0 CH}

01 "

The product was found to be contaminated with trimethylammonium chloride by infrared inspection was: it was purified by using a methanolic solution

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of the crude product through a column with hydroxyl ion exchange resin (50 ml IR 400A) would be performed. After evaporation of the eluent, the purified product is in the zwitterionic form (2) obtained.

“LAHL-y

-OH ₂ 00 U "

00 OH ₂ If

(OH,)·

Paired with the acid form (1), this substance shows a ρΚα value of 8.5

Example 2: Cotton muslin rags are in a 0.5% solution of a standard

alkaline household high-performance detergents and cleaning agents at 60 ⁰ C for 5 minutes, rinsed in tap water and dried. They are then divided into two groups and one group (a). is immersed in tap water and dried. The other group (b) is converted into a 0.1% by weight solution of the quaternary ammonium imide having the formula

e- / Amo μ co Ch ₂ ή (ch ₃ ) ₅

Cl "

(3)

immersed, wherein R is n-dodecyl, the pH-V / er t the Solution is set to 6.5. The ρΚα value of this compound is 8.3. The rags are rinsed in tap water and dried.

Both groups of lobes are then evenly used. an aqueous slurry of crushed garden soil, which comes from a clay soil, soiled and dried. Each group of lobes is then placed in a 0.2% solution

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the same high-performance detergent at 60 ⁰ C for 5 minutes, rinsed in tap water and dried. The solution shows a pH of 10.

The lobes of group (b) are seen to be cleaner than those of group (a).

Example 3: A cotton swab is put in for 3 minutes

a 1% solution of the compound

(3) of Example 2 immersed in tap water. The pH of the solution is 4.2. The rag is then soaked in water rinsed and dried. A comparison rag is dipped in water and dried. The lobes are then turned into a Immersed aqueous dispersion containing 100 parts / million of the dye Chloramine Rose B (color index: Direct Red 31). The rags are rinsed and dried. The cloths pretreated in the solution of the compound of the invention are visibly less colored than those pretreated in water.

Example 4: (a) chloroacetyloctadecanimide.

28.3 g of octadecanamide are treated in 130 ml of benzene with 1 ml of pyridine and the solution is heated to the boil. Then 22.6 g of chloroacetyl chloride are added over the course of 30 minutes and the whole is refluxed for a further 1.5 hours. The solution is allowed to cool to room temperature and after 16 hours 15.5% of white, crystalline product is filtered off. It was confirmed by infrared and nuclear magnetic resonance spectroscopy that the product is chloroacetyloctadecanimide, F. = 105-106 ^° C.

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The reaction takes place according to the equation:

CO BH6 + Cl CO CH ₉ Cl - V C ₁₉ H ,, - COM COCHpCl. (b) Quaternization of chloroacetyloctadecanimide.

1 g of chloroacetyloctadecanimide is dissolved in 50 ml of v / lean acetone dissolved and 5 ml of trimethylamine are added. 16 Hours later, 1.1 g of the precipitated product are filtered off and carefully washed with acetone.

The reaction takes place according to the equation: CONH CO CH ₂ Cl + '™ ^{s w acetone}

COM CO CH ₂ N ⁺ (CH ₅ ) ₅ Cl "

Example 5: In the same way, one obtains through

Treatment of chloroacetyldodecane

imide with pyridine or alkyldimethylamine (C ₁ QH ₅₇ N (CH ₅ ) ₂ ) the following types of compounds:

COM 00 CH ₂ Cl C ₁₁ H ₃₅ CONH CO CH ₂

C ₁₁ H ₂₅ COM CO CH ₂ Cl "^, C ₁₁ H ₃₅ OQNH CO CH ₂ N ⁺ -CH ₅ Cl ~,

^ R ⁼ ift ^ '^ v "''*

Example 6: Test pieces of cotton terry hand

cloths v / ground two pretreatment

v / ash in a standard high-performance synthetic household detergent (Ariel from Procter & Gamble) and then rinsed and dried.

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The test pieces are divided into 2 groups and one group (a) is washed in a 0.55% by weight solution of the same common detergent; the other group (b) is washed in an essentially identical solution, differing only in that 0.025 % of the compound

^C 17 ^H 35 ^{C0 1} ^ ^{C0 CH} 2 are added.

The solutions are made up in hard water (258 parts / million as potassium carbonate). The washing is done in one Miniature washing machine running. The washing conditions are as follows:

10 minutes at 4-9 ° 0,

50 g tissue per "pot ¹¹ in the machine, weight ratio liquid to tissue 20: 1, 2 test pieces per pot, 2 pots each to be compared

Mixture.

After washing, the fabrics are spin-dried, Rinsed twice in cold, hard water (ratio of liquid to fabric 10: 1), spin-dried and in the air dried.

They are subjected to a pairwise comparison for softness by a group of 4 women:

The results in group assessment units (positive preferred) were as follows:

Group (a) -0.4-6 Group (b) +0.52.

Least significant difference Ό, 7 & (95% reliability).

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Example 7: Preparation of chloroacetylacetamide.

6.0 g of chloroacetamide, 9.0 g of acetic anhydride and 0.6 ml Acetyl chloride is refluxed for 1 hour. 25 ml of benzene are added to the cooled solution. After 2 hours it will the precipitated product is filtered off, washed with light gasoline and dried. The yield is 5> 7 g and the chlorine. acetylacetamide shows a P. = 103 - 105 ° 0. (The method is adapted from that of Polya and Spotswood, Recueil 1948, 67, p. 927.)

Quaternization of chloroacetylacetamide.

1 g of chloroacetylacetamide and 2.5 g of octadecyldimethylamine are refluxed in 10 ml of acetone for 1.5 hours. After cooling, the quaternary ammonium imide (1) is precipitated and separated off by filtration. The yield is 2.4 g. The product is water-soluble, gives a foaming solution and shows positive reaction with regard to ionic Chloride. The infrared spectrum was in agreement with that attributable to the following structure:

CH, CO NH CO CH ₂ N ⁺ (CH,) ₂ Cl "(1).

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Claims (13)

42653 claims: 1. Quaternary ammonium imides of the general formula -R, 00 N "CO'GH- N ^l 3 or their cationic adducts of the general formula CO m CO CH ₂ N- - ^R 3 ^{> R} 4 X an anion, R _{1 is} an alkyl group with 1 to 25 carbon atoms or a phenyl or a benzyl group or an alkylbenzyl or alkylphenyl group with 8 to 18 carbon atoms in the alkyl radical, R _{2 is} an alkyl group with 1 to 26 carbon atoms or a benzyl or phenyl radical, Each of the radicals R- * and R ^, an alkyl group with 1 to 4 carbon atoms or a phenyl or benzyl radical or R ₂ , R, and R taken together represent a pyridine ring and one or both radicals R ₁ and R _{2 are} at least 10 carbon atoms contain, symbolize. 2. A compound according to claim 1, wherein R _{1 is} an alkyl group with 13 to 21 carbon atoms or an alkylbenzyl or alkylphenyl group with 12 to 14 carbon atoms in the alkyl chain. 209881/0727 4-2658 3. Connection to. Claim 1 or 2, wherein each of Radicals Rp, R * and R ^, symbolize a methyl or ethyl group. 4 ·. A compound according to claim 1 or 2, wherein R ₂ , R 3 ^{and <3} · R. together symbolize a pyridine ring. 5. "The compound of claim 1, wherein R _{2 is} an alkyl group having 14 to 22 carbon atoms. 6. Connection according to claim 5? wherein each of the remainders R, and R ^ is a methyl or ethyl group. 7 · Compound according to claim 5 or 6, wherein R ^, a methyl or ethyl group. 8. The composition of soaking fabrics, characterized in that it contains 1 to 7 includes a compound of any of arrival _v sayings in cationic form. 9. Composition according to claim 8, characterized in that that it also contains a nonionic or zwitterionic surfactant. 10. Composition suitable as an additive for rinsing textiles, characterized in that it contains a compound according to any one of claims 1 to 7 and a pH-buffering Contains agent, at least 0.1 wt .- ^ of the compound is in its cationic form and the pH of the entire solution is no more than 2 units above the ρΚα value of the surfactant. 11. Alkaline detergent composition containing builders, characterized in that. they a connection u .-. cii any one of claims 1 to 7, an anionic organic detergent and contains alkaline builder salts. 209881/0727 12. Composition according to claim 11, characterized in that that it also contains a nonionic or zwitterionic surfactant. 13. Composition according to claim 11 or 12, characterized in that the weight ratio of builder salt to organic surfactant is 1: 4 to 30: 1. For: The Procter & Gamble Company CincinnatiAOhio), V.St.A, - Dr. «. J. WoIH Lawyer 20 98 8 1/0727