EP0530278A1

EP0530278A1 - New nitrogen containing compounds, a process for their preparation and use of the compounds

Info

Publication number: EP0530278A1
Application number: EP91910106A
Authority: EP
Inventors: Claes Göran AXBERG; Bengt-Arne Thorstensson; Jan Walding
Original assignee: Berol Nobel AB
Current assignee: Nouryon Surface Chemistry AB
Priority date: 1990-05-23
Filing date: 1991-05-15
Publication date: 1993-03-10
Also published as: CN1056682A; AU7904291A; FI925300A0; WO1991017975A1; ZA913719B; BR9106444A; CA2083503A1; JPH0819619B2; FI925300A; JPH05505621A; HU9203660D0; SE9001862D0

Abstract

L'invention concerne des composés d'amines tertiaires et des composés d'ammonium quaternaire qui se caractérisent par le fait qu'ils contiennent deux plus longs groupes alkyle ou alcényle et au moins un groupe ester qu'on peut hydrolyser et qui peut donc conférer aux composés un caractère ionique différent de celui d'origine. Les composés d'amines tertiaires et les composés d'ammonium quaternaire sont utiles, entre autre choses, en tant que bactéricides et assouplissants pour les textiles. Les composés d'amines tertiaires et les composés d'ammonium quaternaire correspondent respectivement aux formules générales (I) et (II), où R représente un groupe alkyle ou alcényle droit ou ramifié ayant de 7 à 24 atomes de carbone, R1 représente un groupe alkyle ayant de 1 à 4 atomes de carbone, n est un entier variant de 1 à 4 et R' et R'' représentent indépendamment l'un de l'autre, hydrogène, des groupes alkyle ou des groupes hydroxy-alkyle ayant de 1 à 3 atones de carbone ou des groupes hydroxyle, m vaut 0 ou 1 et A représente un groupe renfermant ester ou un groupe contenant une fonction amido et est un groupe 1) -(O-CH2-CHR''')p-O-C(O)-(CH2)q-, 2) -C(O)O-CHR'''-CH2-(O-CHR'''-CH2)p-, (3) -(O-CH2-CHR''')p-O-C(O)-O-CHR'''-CH2-(O-CHR'''-CH2)p-, (4) -C(O)-O-CH2-C(OH)H-CH2- ou 5) -C(O)-NH-(CH2)z-, dans lequel R''' représente hydrogène ou un groupe méthyle, p varie de 0 à 5, q vaut 1 ou 2 et z vaut 2 ou 3, ce qui fait que, par conséquent, le nombre total de groupes alkylénéoxyde dans les groupes de type 3 ne dépasse pas 5, R2 représente un groupe alkyle ou hydroxyalkyle ayant de 1 à 4 atomes de carbone et X représente un anion.The invention relates to tertiary amine compounds and quaternary ammonium compounds which are characterized in that they contain two longer alkyl or alkenyl groups and at least one ester group which can be hydrolyzed and which can therefore confer to the compounds an ionic character different from that of origin. Tertiary amine compounds and quaternary ammonium compounds are useful, among other things, as bactericides and fabric softeners. The tertiary amine compounds and the quaternary ammonium compounds correspond respectively to the general formulas (I) and (II), where R represents a straight or branched alkyl or alkenyl group having from 7 to 24 carbon atoms, R1 represents a group alkyl having 1 to 4 carbon atoms, n is an integer varying from 1 to 4 and R 'and R' 'independently of each other represent hydrogen, alkyl groups or hydroxy-alkyl groups having from 1 with 3 carbon atoms or hydroxyl groups, m is 0 or 1 and A represents an ester-containing group or a group containing an amido function and is a group 1) - (O-CH2-CHR '' ') pOC (O) - (CH2) q-, 2) -C (O) O-CHR '' '- CH2- (O-CHR' '' - CH2) p-, (3) - (O-CH2-CHR '' ') pOC (O) -O-CHR '' '- CH2- (O-CHR' '' - CH2) p-, (4) -C (O) -O-CH2-C (OH) H-CH2- or 5 ) -C (O) -NH- (CH2) z-, in which R '' 'represents hydrogen or a methyl group, p varies from 0 to 5, q is 1 or 2 and z is 2 or 3, which makes that, therefore, the total number of alkyleneoxide groups in type 3 groups do not exceed 5, R2 represents an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and X represents an anion.

Description

New nitrogen containing compounds, a process for their preparation and use of the compounds

The present invention relates to new tertiary amines and to new quaternary ammonium compounds. More particularly the invention relates to new such compounds which are characteristic in that they contain two longer hydrophobic hydrocarbon groups and at least one ester group which can be hydrolysed thereby conferring to the compounds a differ¬ ent ionic character than the original one. The invention also relates to a method for the preparation of the new compounds, to the use of the compounds, among other things as conditioning agents for textiles, and to compositions containing the compounds.

Tertiary amines and quaternary ammonium compounds containing two longer hydrophobic hydrocarbon groups, alkyl and/or alkenyl groups, are per se well-known^' compounds and known for use as, among other things, bactericides and textile softeners. Didecyl dimethyl ammonium chloride is often used as bactericide and the compound most commonly used as textile softener is di-(hydrogenated tallow alkyl) dimethyl ammonium chloride, which has a very satisfactory textile softening effect. Quaternary ammonium compounds of this type and the corresponding tertiary amines are, however, less advantageous from a biological point of view due to their slow degradation and to a certain toxicity to aquatic organisms.

The present invention relates to new tertiary amines and quaternary ammonium compounds which are characteristic in that they contain two longer hydrophobic hydrocarbon groups and at least one ester group which can be hydrolyzed and as hydrolysis product hereby confer to the nitrogen containing compounds another ionic character than the original one. The nitrogen containing hydrolysis products have a substantially lower toxicity to aquatic organisms. The present invention thus relates to new tertiary amines and quaternary ammonium compounds as defined in the patent claims. The compounds can be characterized by the general formulae ), respectively,

Both in the tertiary amines of formula (I) and the quaternary ammonium compounds of formula (II) R are alkyl or alkenyl groups having from 7 to 24 carbon atoms, or from 8 to 24 carbon atoms when the compounds do not contain groups A or other substituents, which can be straight or branched, and R_j_ is an alkyl group with l to 4 carbon atoms. The ester group —C(O)—0— τ_ can be hydrolyzed to —C(0)—0^~ whereby compounds of different ionic character are obtained. The tertiary amines of formula (I)^■ containing the ester group are in themselves slightly cationic at normal pH values since they are protonated at a pH below about 9. Compounds of ampholytic character, ie compounds which, dependent on the pH, have a net charge which is positive, zero or negative, are obtained at hydrolysis. The quaternary ammonium compounds of formula (II) are cationic and give at the ester hydrolysis the corresponding struc¬ ture of betaine type, ie compounds of the formula

The new compounds can thus be used in the form wherein they have the desired affinity to the substrates which are considered by being cationic and then, after use, at a pH change be transformed into compounds which do not have cationic character and which thereby are considerably less toxic to aquatic organisms such as fish, daphnia, algae etc.. The compounds of the present invention have bac¬ tericidal and conditioning effect through the two groups R which are longer, straight or branched, alkyl and/or alkenyl groups. The groups R can also be substituted and contain a hydroxyl group as a substituent and optionally also contain an ether bond. Of the compounds according to the present invention the quaternary ammonium compounds are preferred. When the compounds are intended for use primar¬ ily for bactericidal effect the two groups R are both suitably alkyl groups with 7 to 12 carbon atoms, or 8 to 12 carbon atoms for compounds which do not contain groups A or other substituents. When they are to be used primarily for conditioning, especially softening, effect the groups R are suitably alkyl or alkenyl groups with 13 to 22 carbon atoms, or from 14 to 22 carbon atoms for compounds which do not contain groups A or other substituents. It is of course

•comprised within the definitions that the R groups can be technical mixtures of alkyl and/or alkenyl .group^'s with different number of carbon atoms originating from natural materials such as tallow, hydrogenated tallow, palm oil, coconut oil, palm kernel oil etc.. Another very suitable natural material is rapeseed oil which gives fatty acid groups with mainly C18 groups. R]_ is an alkyl group with 1 to 4 carbon atoms, such as a methyl-, ethyl-, propyl- or isopropyl group. The hydrocarbon chain between the nitrogen and the ester group in the compounds is the group -(CR'R^{, ,})_n- where n is an integer of 1 to 4 and R'^" and R' ' independent of each other are hydrogen, alkyl- or hydroxy¬ alkyl groups with 1 to 3 carbon atoms or hydroxyl groups. The group -(CR'R¹')_!}- may also be a group substituted with an oxo group, and then preferably the group -(CH2~C(0)- CH2)-. The group -(CR'R'')_n- is suitably a straight, unsub- stituted alkylene group with 1 to 4 carbon atoms or such a group substituted with an alkyl, hydroxyalkyl or hydroxyl group. It is preferred that the nitrogen atom in the compounds and the ester group in question are separated by a straight alkylene group with 1 to 4 carbon atoms and particularly by a ethylene group. In the quaternary ammonium compounds of formula (II) R2 is an alkyl or hydroxyalkyl group with 1 to 4 carbon atoms. R is suitably a methyl group or a hydroxyethyl group, preferably a methyl group. X in the quaternary ammonium compounds is an anion. X can be any anion which does not have a negative influence on the effect of the compounds in the particular use of them. Suitable anions are halides, especially chloride and bromide, alkyl sulfates such as methyl sulfate and ethyl sulfate, alkyl phosphates such as dimethyl phosphate. Chloride ions are the preferred anions. The tertiary amines can of course, as is conventional, be in the form of salts, of inorganic or organic acids, for example in the form of hydrochlorides or acetates.

A in the tertiary amines and the quaternary ammonium compounds represents a group containing an ester function or an amido function, which can be present in the com¬ pounds. Thus m is 0 or 1. The compounds according to the invention can, if they contain groups A, contain one or two such groups. The groups A can be four different types of groups containing an ester function or a group containing an amido function according to the following:

1) -(0-CH₂-CHR"')_p-0-C(0)-(CH₂)_q-

2) -C(0)0-CHR' ' '-CH₂-(0-CHR' ' '-CI^p-

3) -(0-CH₂-CHR' ' ^• )p-O-C(0)-O-CHR' ' ^•-CH₂-(O-CHR' ' '-CH₂)_p- 4) -C(0)-0-CH₂-C(OH)H-CH₂-

5) -C(0)-NH-(CH₂)_z- wherein R' ^• ' is hydrogen or a methyl group, p is 0 to 5, q is 1 or 2 and z is 2 or 3, whereby, however, the total number of alkyleneoxide groups in groups of type 3 does not exceed 5.

Compounds containing ester groups A can be hydrolyzed also at this ester group and give a primary degradation of the compounds to smaller structures which is of interest with regard to biological degradability. If the compounds contain groups of type 2, 3 or 4 there will, at hydrolysis of this ester group, be no change of charge character of the after hydrolysis of the ester group -0-C(0)-R₁ obtained nitrogen containing hydrolysis product. If the compounds contain a group A of type 1 a hydrolysis product with anionic charge will be obtained at hydrolysis. If the compounds contain an ester group A it is thus preferred that this is of type 2, 3 or 4. An advantage is, however, also obtained with groups of type 1 in comparison with the original cationic compounds, since anionic compounds generally are less toxic than cationic. The quaternary ammonium compounds can also contain one A group which is an ester containing group and one A group which contains an amido function. As examples of quaternary ammonium com¬ pounds containing a hydroxyl substituent can be mentioned compounds of formula [R_χ-CH(OH)-CH₂] (CR'R")_n-C(0)-0-R₁ X^" (III) wherein R_x is an alkyl or alkenyl group with from 6 to 22 carbon atoms, and particularly those wherein R' and R' ' are hydrogen, n is 1, τ_ and R2 and X are as earlier defined. As examples of quaternary ammonium compounds containing ether bonds and hydroxyl groups can be mentioned those of formula [R-0-CH₂-CH(OH)-CH₂] (CR'R' ' )_n-C(0)-0-Rχ X^~ (IV) wherein R is a previously defined and particularly those wherein R' and R' ' are hydrogen, n is 1, R_]_ and R2 and X are as earlier defined. As examples of quaternary ammonium compounds containing an A group of type 5), ie an amido function, can be mentioned those of formula

[R-CNH-(CH₂)₂ ")n-^c(°)-0-Rι X^" (V) wherein R is as previously defined and particularly those wherein R¹ and R' ' are hydrogen, n is 1, R_]_ and R2 and X are as earlier defined. As examples of quaternary ammonium compounds containing a group A of type 4 can be mentioned those of formula

[R-C ?-0-CH₂-CH^H-CH₂]2 ^* )n"^c(°)-°^~R1 ^x~ (^VI) wherein R is as previously defined, and particularly those wherein R' and R' ' are hydrogen, n is 1, Rj_, and R2 and X are as earlier defined.

However, with regard to preparation techniques, economy and efficiency at use, compounds which do not contain groups A are preferred. For these reasons the most preferred compounds are such which do not contain groups A and which contain unsubstituted R groups.

As stated, the quaternary ammonium compounds are preferred, but all details on substituents etc. given above and in the following are of course also applicable to the amines. It is particularly preferred that the compounds contain a methyl group as group R_j_, since it has been found that the compounds then undergo hydrolysis more rapidly thus giving more rapid toxicity decrease. At the preparation of the compounds a certain trans-esterification will occur so that the product may also contain Rη_ groups originating from the used solvent, such as isopropyl groups or ethyl groups. By use of eg shorter reaction times, lower temperatures etc transesterification can be controlled and yield of product with desired group increased. To avoid trans-esterification the reaction can also be carried out in an inert solvent, eg methyl ethyl ketone. Desired R_j_ group in compounds can also be obtained using solvent giving trans-esterification with the same R^_ group. The tertiary amines according to formula I can be prepared by reaction between secondary amine, with the formula [R-(A)_m]2-NH, wherein R, A and m have the above given definitions and an alkyl ester of an unsaturated carboxylic acid of the formula H₂C=CR'-(CR'R' ' )₀_2-CCORι, wherein R' , R' ' and R_]_ are as defined above. The reaction can be carried out at temperatures of from about 50°C to about 150°C and during times of from about 12 hours to about 48 hours. The reaction is suitably carried out in a solvent selected from groups lower alcohols, such as ethanol and isopropanol, glycols, polyglycols and glycol ethers. The tertiary amines can be used as such, or in the form of salts, for the given purposes.

The tertiary amines are also intermediates for the preparation of the quaternary ammonium compounds according to the invention. The tertiary amines can hereby be quater- nized, with conventional quaternizing agents such as methyl chloride, methyl bromide, dimethyl sulfate, diethyl sul¬ fate, to quaternary ammonium compounds of formula II. Alternatively, the quaternary ammonium compounds can be prepared from tertiary amines of the formula [R-(A)_m]2-NR2 which are quaternized by reaction with an alkyl ester of haloalkanoic acid, or substituted haloalkanoic acid, of the formula X-(CR'R' ' )_nCOORτ_, wherein R]_, R' , R' ' and n have the above given definitions and X is a halogen, preferably chlorine. Suitable reaction conditions and solvents are those given for the reaction between secondary amine and alkyl ester of unsaturated carboxylic acid. The reaction times can, however, usually be kept within the range of from about 2 hours to about 24 hours. Methods for the preparation of amines containing the ester groups A are well known to the man skilled in the art. As some typical examples of the preparation of tertiary amines containing groups A as above identified can be mentioned reaction between methyl imino diacetic acid and a fatty alcohol for groups A of type 1), reaction between methyl diethanol amine and fatty acids, or fatty acid esters, such as methyl esters or triglycerides, for groups A of type 2) and reaction between methyl diethanol amine and fatty alkyl chloroformiate for group A of type 3) . Quaternary ammonium compounds of formula (III) can for example be prepared by reacting a lower alkylamine, for example methylamine, with α-epoxides with longer aliphatic groups and subsequent quaternization of the obtained tertiary amine with alkyl ester of haloalkanoic acid, or substituted haloalkanoic acid. Quaternary ammonium compounds of formula (IV) can be prepared by reaction between fatty alcohol and epichloro- hydrin. The obtained reaction product is then reacted with lower alkylamine followed by quaternization with alkyl ester of haloalkanoic acid, or substituted haloalkanoic acid. Quaternary ammonium compounds of formula (V) can for example be prepared by the reaction of aminoethyl ethanol amine or diethylene triamine and fatty acids or fatty acid esters, such as methyl esters or triglycerides. The thus obtained reaction product is then reacted with ethylene oxide and is subsequently quaternized with an alkyl ester of a haloalkanoic acid, or substituted haloalkanoic acid. Quaternary ammonium compounds of formula (VI) can for example be synthesized by reaction between epichlorohydrin and fatty acids or fatty acid esters, eg methyl esters or triglycerides. The thus obtained products are then reacted with a lower amine, such as methyl amine, and are sub¬ sequently quaternized with an alkyl ester of haloalkanoic acid, or substituted haloalkanoic acid. Quaternary ammonium compounds containing a group -(CR'R'')_n- which is sub¬ stituted with an oxo group, preferably the group -(CH2- C(0)-CH₂)-, can be produced by reaction of a dialkyl methyl amine with methyl-4-halo-3-oxo-butanoate. At the production of the present amines and quaternary ammonium compounds a certain hydrolysis of the formed ester product may occur. However, it has been found that this does not impair the efficiency of the product at use. Even fairly high amounts,^' of up to about 50 to 70 per cent of hydrolysis product, based on dry substance in the reaction product, do not seem to impair the effect in use, as shown in the examples. The present compounds can thus be used as produced, ie as obtained reaction mixture containing hydrolysis product. The invention also relates to reaction mixture products produced as disclosed above. The obtained reaction mixture products can also contain amines or quaternary ammonium compounds, respectively, which do not contain the ester group, as the compounds of the present invention do. The presence of such compounds do not have a negative influence on the effect at use, but it is of course desired to suppress the amounts of such compounds in order to get as good properties as possible with regard to environmental properties, ie degradation and toxicity.

The present invention also relates to the use of the ertiary amines, the quaternary ammonium compounds and the reaction mixture products of the above given definitions as bactericides and as conditioning agents, ie as agents whic confer antistatic and/or softening effect. As conditioners the compounds are primarily used for textile materials, and especially for the softening effect they give, but they ca also be used in hair care products, in which a softenin and/or antistatic effect is often desired. For bactericidal use compounds wherein R are alkyl groups with 7 to 12, or 8 to 12, carbon atoms are preferably used, while it for use as conditioners is preferred to use such compounds in which the R groups are alkyl and/or alkenyl groups with 13 to 22, or 14 to 22, carbon atoms. The compounds are employed in conventional manner in the given fields of utilization. As bactericides the compounds can be used for example in the food industry and in hospitals for disinfection of equip- ment. They are hereby used in aqueous solutions and often combined with nonionic tensides in order that also a cleaning effect will be obtained. When the compounds are used as conditioners for textile materials they.are like¬ wise used in conventional manner. Textile softeners are normally added to the rinsing water after washing in the form aqueous or water/solvent containing formulations, to a dosage corresponding to up to about 5 g active substance per kg dry material, and allowed to have effect on the textile materials during shorter periods of time, usually from 5 to 10 minutes. The compounds according to the invention should suitably at use be added by means of an aqueous formulation which has a pH value not exceeding 4.5. The pH is suitably within the range of from 2.0 to 4.5 and preferably within the range from 2.5 to 4. At these pH values the compounds are essentially present in the form in which they have affinity to the treated materials, as discussed above. When the compounds after the use are discharged -with the waste water the desired ester hydro¬ lysis to compounds of other ionic character, which is advantageous with regard to toxicity, is obtained.

The invention also relates to compositions containing the new compounds which are particularly suitable for use as textile softeners. The compositions are water and/or solvent containing formulations containing the active compounds, suitably in an amount of at least 1 per cent by weight. The compositions can either be concentrated pro¬ ducts which contain higher amounts of active substance, suitably from about 50 to about 90 per cent by weight, in solvent or a mixture of water and solvent. Solvents are here primarily such which have been used at the preparation of the compounds, ie lower alcohols, such as ethanol and isopropanol, glycols, polyglycols and glycol ethers, or other suitable solvents, inert or others, as discussed earlier. The compositions can also be diluted products intended for direct used. The compositions in this case suitably contain the compounds in amounts of from 1 to about 40 per cent by weight and are aqueous formulations, which may also contain solvents, suitably such as mentioned above, in smaller amounts, such as up to 20 per cent by weight based on the combination of active substance and water. Compositions containing water or water and solvent should suitably have the above given pH values so that the compounds will not undergo any substantial hydrolysis in the compositions. At dilution with water a pH below 4.5 is usually obtained. Mineral acids, such as hydrochloric acid and sulfuric acid, as well as organic acids, such as for example lactic acid, citric acid and benzoic acid, can be added to adjust the pH to the desired value. The composi¬ tions containing water or water and solvent can of course also contain other per se known softeners and for this type of product conventional additives such as emulsifiers, vis¬ cosity modifiers which for example can be inorganic elec- trolytes such as sodium chloride or calcium chloride, dye, perfumes, foam suppressing agents, optical brighteners etc The invention is further illustrated in the following examples. Parts and per cent relate to parts by weight and per cent by weight, respectively, unless otherwise stated. Example 1

328 grams of di-(hydrogenated tallow alkyl) methyl amine with a total amine number of 71.7 mg HCl/g were mixed with 135 grams of isopropyl alcohol. The mixture was then heated to 90°C and 76 grams of monochloro acetic acid methyl ester were added to the mixture during one hour. The temperature was then increased to about 100°C and kept at that value for a period of 7 hours. The resulting product had a total amine number of less than 1 compared to 50.9 for the original amine/isopropanol mixture, a dry solids content of 75.6% and contained 25.4% dialkylbetaine iso- propyl ester, 20.0% dialkylbetaine methyl ester, 5.6% dialkylbetaine and 3.6% unreacted dialkyl methyl amine. Example 2

The softening effect of the reaction product in example 1 was evaluated by treating clean cotton terry towels with aqueous dispersions of the reaction product and with di-(hydrogenated tallow alkyl) dimethyl ammonium chloride (DHTDMAC) , respectively. The dispersions contained an amount of product corresponding to 0.5 grams of dry• substance per kg of textiles. The treatment of the towels was carried out under agitation during 5 minutes, after which time the towels were dried. A reference sample was included, treated in the same way as above, but with pure water only.

The evaluation of softness was made on a scale of 0 to 5, where 5 represents the softest feel, and was carried out by a panel of 12 people. The result of the panel's evaluation of the above treatments were as follows:

Product Softness score

Example 1 5

DHTDMAC 5 Untreated reference 0

This example shows that the present products give as good softening effect as the dominating commercial product

DHTDMAC.

Example 3 A part of the reaction product in example 1 was hydrolysed by dispersion in water at a concentration of 5% dry substance and subsequently increasing the pH of the dispersion to 10 and the temperature to 60°C for 2 hours.

The organic material, now containing the dialkyl betaine and only trace amounts of the dialkyl betaine ester, was then extracted into an organic phase, separated off, evaporated to dryness and diluted with isopropyl alcohol to

75% dry substance. The thus hydrolysed product was mixed with the original reaction product from example 1 in different ratios and the mixtures were used as aqueous dispersions for testing of their softening effect as described in example 2. DHTDMAC was included as a reference. The results were as follows:

Product Softness score

DHTDMAC 4.9

Example 1/Hydrolysed example 1 100:0 4.2 Example 1/Hydrolysed example 1 75:25 5.0 Example 1/Hydrolysed example 1 50:50 4.3 Example 1/Hydrolysed example 1 75:25 1.7

In view of the inherent precision of the evaluation method, there is no significant difference in softness between the top four treatments in this test. Example 4

60.8 grams of a di-(hydrogenated rapeseed alkyl) methyl amine were mixed with 13.6 grams of isopropyl alcohol in a closed reactor. Subsequently 12.9 grams of the methyl ester of monochloro acetic acid were added. The temperature was increased to 80°C and the temperature was then kept constant for 24 hours. The total amine number of the reaction product was then 2.1 compared to 51.0 for the initial amine/isopropanol mixture. The resulting product had a dry solids content of 84.9% and contained 14.6 % di¬ alkylbetaine isopropyl ester, 28.0% dialkylbetaine methyl ester, 9.8% dialkylbetaine and 5.4% unreacted dialkyl methyl amine. Example 5 The product in example 4 was tested for acute toxi¬ city to Daphnia magna according to OECD Guideline No 202, and was found to have a 48 hours EC50 value of 10 ppm.

For comparison, a 78% active sample of the most common textile softener raw material, di-(hydrogenated tallow alkyl) dimethyl ammonium chloride, was subjected to the same test and was found to have a 48 hours EC50 value of 0.45 ppm.

As evident, the product of the present invention had about 20 times lower toxicity than DHTDMAC. Example 6

680 grams of a di-(hydrogenated rapeseed alkyl) methyl amine were mixed with 149 grams of isopropyl alcohol in a closed reactor. Subsequently 136 grams of the methyl ester of monochloro acetic acid were added. The temperature was increased to 80^βC and the temperature was then kept constant for 20 hours. The total amine number of the reaction product was then 3.4 compared to 54.5 for the initial amine/isopropanol mixture. The reaction product was cooled down and a further 123 grams of isopropanol were added, giving a product with a dry solids content of 75.3% and containing 16.0% dialkylbetaine isopropyl-ester, 32.3% dialkylbetaine methyl ester, 4.5% dialkylbetaine and 2.7% unreacted dialkyl methyl amine.

Example 7

The product in example 6 was tested for acute toxi¬ city to Rainbow Trout (Oncorhynchus mykiss) in a semistatic test according to OECD Guideline No 202, and was found to have a 96 hours LC_5Q value as high as 19 ppm.

The product was tested also for acute toxicity to a green alga (Scenedesmus subspicatus) according to OECD Guideline No 201, and was found to have a 96 hours EJ-_JCS value of 24 ppm (biomass) and an E_rC₅o (24-48 hours) of 33 ppm (growth rate), which values are very good. Example 8

This example shows a simulated primary degradation. An aqueous dispersion made from the reaction product in example 6 and containing 0.5% dry solids was adjusted to pH 7 with a potassium hydroxide solution and was kept at that pH by means of a pH-stat unit providing intermittent addition of potassium hydroxide solution as needed to keep the pH constant. Samples were taken at intervals and the relative amounts of dialkyl betaine and dialkyl betaine esters were determined. The results were as follows:

Time, hours Betaine esters, rel. % Betaine, rel. %

0 71 29

1 56 44 2 51 49

8 38 62

24 27 73

48 20 80 56 18 82

120 14 86

Example 9

This example shows the preparation of a quaternary ammonium compound containing a group A containing an ester group. 105.8 grams of a diester amine obtained by reaction of 1 mole of methyl diethanol amine and 1.85 moles of tallow fatty acid and with a total amine number of 66.0 were mixed with 48 grams of isopropyl alcohol in a closed reactor. Subsequently 30 grams of the methyl ester of monobromo acetic acid were added. The temperature was increased to 60°C and the temperature was then kept con¬ stant for 20 hours. At this point a further 0.6 grams of methyl ester of monobromo acetic acid were added and the reaction continued for 5 hours. The total amine number of the reaction product was then 3.6 compared to 45.4 for the initial amine/isopropanol mixture. Example 10

To 100 grams of a didecyl methyl amine with a total amine value of 117.3 were added 45.0 grams of methanol and 39.4 grams of the methyl ester of monochloro acetic acid in a closed reactor. The temperature of the mixture was in¬ creased to 100°C and was then kept constant for 5 hours. At this point, the total amine number of the mixture was 3.8 compared to 80.9 for the initial amine/methanol combina- tion. Analysis showed a ratio of dialkyl betaine methyl ester to dialkyl betaine of about 10:1. Examole 11

The reaction mixture obtained in example 10 was evapo¬ rated under vacuum to total dryness and subsequently diluted with isopropanol to 50% dry solids content. The bactericidal effect of this product against Escherichia coli NCTC 8196 was then evaluated in a modified B.S. 3286 suspension test in an aqueous medium containing 300 ppm hardness according to A.O.A.C. (Official Methods of Analysis of the Association of Official Analytical Chemists). It was found that a kill in excess of 99.999% was obtained at a dosage level of 100 ppm of active matter as dry solids. Example 12

This example shows the preparation of pure methyl ester quaternary ammonium compound. 152 grams of di- (hydrogenated tallow alkyl) methyl amine with a total amine number of 71.6 mg HCl/g were mixed with 83 grams of methanol. The mixture was then heated to 60°C and 42 grams of monochloro acetic acid methyl ester were added. The temperature was increased to about 90°C and the reaction mixture was refluxed for 11 hours, after which time additionally 2 grams of monochloro acetic acid methyl ester were added and the reaction mixture was refluxed for another 2 hours. The resulting product had a total amine number of 3.7, a dry solids content of 68.9% and contained 60.9% dialkylbetaine methyl ester, 2.5% dialkylbetaine and 2.8% unreacted dialkyl methyl amine. Example 13

149 grams of di-(hydrogenated tallow alkyl) methyl amine with a total amine number of 71.6 mg HCl/g were mixed with 86 grams of isopropanol. The mixture was then heated to 75^CC and 51.5 grams of monochloro acetic acid isopropyl ester were added. The temperature was increased to about 90°C and the reaction mixture was refluxed for 6 hours. The resulting product had a total amine number of 3.9 and contained 67.7% dialkylbetaine isopropyl ester and 3.0% unreacted dialkyl methyl amine. Example 14

The reaction mixtures obtained in Examples 12 and 13 were tested for acute toxicity to Daphnia magna according to OECD Guidelines No. 202 with the following result: Product ECςn, 48 hours

Example 12 7.0 ppm

Example 13 0.75 ppm Example 15

The softening effect of the reaction mixtures obtained in examples 12 and 13 was tested according to the procedure in example 2 with DHTDMAC as a reference at a common dosage rate of 0.5 grams of dry solids per kg of textiles. An untreated reference was also included in the test. The results were found to be as follows: Product Softness score

Example 12 5 Example 13 5

DHTDMAC 5

Untreated reference 0 Example 16

This example shows the preparation of a quaternary ammonium compound of formula (VI). 100.4 grams of an epoxide (84.1% active), obtained by the reaction of an aliphatic alcohol having a C16 to C20 chain sold under the trade name Alfol 1620 and epichlorohydrin, were heated to 50°C and flushed with nitrogen. 12.4 grams of methyl amine (as 33% in ethanol) were added slowly during 3 hours while the temperature was kept between 45 and 60°C. The tempera¬ ture was then kept at 60°C during 4 hours, at which time additionally 0.22 grams of methyl amine (as 33%) were added and the reaction was continued for another 4.5 hours. The obtained reaction mixture containing the desired di-(3- alkoxy-2-hydroxypropyl) methyl amine had a total amine value of 42.1 mg HCl/g.

20 grams of the above obtained reaction product were mixed with 5.8 grams of isopropanol and heated to 80°C and then 3.36 grams of monochloro acetic acid methyl ester were added. The mixture was refluxed at 90°C for 10 hours, after which time an additional 0.26 grams of monochloro acetic acid methyl ester were added and the reaction mixture was refluxed for further 3 hours. The reaction product obtained had a total amine number of 3.6 mg HCl/g.

Claims

Claims 1. Tertiary amines and quaternary ammonium compounds, respectively, characterized in that they have the general formulae

R-(A)m- N— ^•((CCRR'^IRR'^, '^I))_n Λ—C—0—Ri (I), and

X^" (II), respectively, wherein R are straight or branched alkyl or alkenyl groups with 7 to 24 carbon atoms, R_j_ is an alkyl group with 1 to 4 carbon atoms, n is an integer of 1 to 4 and R' and R' ' independent of each other are hydrogen, alkyl- or hydroxy¬ alkyl groups with 1 to 3 carbon atoms or hydroxyl groups, m is 0 or 1 and A is a group containing an ester group or a group containing an amido function and is a group

1) -(0-CH₂-CHR' ' ' )_p-0-C(0)-(CH₂)q-

2) -C(0)O-CHR' ' ^■ -CH₂-(O-CHR' ' '-CH₂)_p-

3) -(0-CH₂-CHR' ' ' )p-O-C(0)-O-CHR' ' '-CH₂- (O-CHR' ' ' -CH₂)_p- 4) -C(0)-0-CH₂-C(OH)H-CH₂- or

5) -C(0)-NH-(CH₂)_z- wherein R' ' ' is hydrogen or a methyl group, p is 0 to 5, q is 1 or 2 and z is 2 or 3 , whereby, however, the total number of alkyleneoxide groups in groups of type 3 does not exceed 5, R₂ is an alkyl or hydroxyalkyl group with 1 to 4 carbon atoms and X is an anion.

2. Compounds according to claim 1, characterized in that both R' and R' ' are hydrogen.

3. Compounds according to claim 1 or 2, characterized in that m is 0 or m is 1 whereby A is the group

-C(0)0-CHR' ' '-CH₂-(O-CHR' ' '-CH₂)_p- , the group

-(0-CH₂-CHR' • ' )_p-0-C(0)-O-CHR' ^• '-CH₂-(O-CHR' ' '-CH₂)_p- or the group -C(0)-0-CH₂-C(OH)H-CH₂- .

4. Compounds according to any of claims 1 to 3, characterized in that R_x is a methyl group, an ethyl group or an isopropyl group.

5. Compounds according to any of claims 1 to 4, characterized in that R_]_ is a methyl group.

6. Compounds according to any of the preceding claims, characterized in that they are quaternary ammonium compounds wherein the groups R are alkyl or alkenyl groups with 7 to 24 or 8 to 24 carbon atoms.

7. Compounds according to claim 6, characterized in that m is 0 and the groups R are alkyl or alkenyl groups with 14 to 22 carbon atoms.

8. A process for the preparation of tertiary amines as defined in claim 1, characterized in that a secondary amine, with the formula [R-(A)_m]₂NH, wherein R, A and m have the corresponding meanings as for the tertiary amines, is reacted with an alkyl ester of an unsaturated carboxylic acid of the formula H₂C=CR'-(CR'R' ' )o-₂-^COORi/ wherein R' _f R¹ ' and Ri have the corresponding meanings as for the tertiary amines.

9. A process for the preparation of quaternary ammonium compounds as defined in claim 1, characterized in that tertiary amines as defined in claim 1 are quaternized with conventional quaternizing agents or, alternatively, that tertiary amines with the formula [R-( )_m]2-R2, wherein R, A, m and R₂ are as defined in claim 1, are quaternized by reaction with an alkyl ester of a haloalkanoic acid, or substituted haloalkanoic acid, with the formula X- (CR'R¹ ' )_nCOORι, wherein R_]_, R' , R' ' and n have the corre¬ sponding meanings as for the quaternary ammonium compounds and X is a halogen.

10. A solvent containing reaction mixture product, characterized in that it is the product of a quaternization reaction of tertiary amines as defined in claim 1 with conventional quaternizing agents or, alternatively, the reaction product of tertiary amines with the formula [R-(A)_m]₂NR₂, wherein R, A, m and R₂ are as defined in claim 1, and an alkyl ester of a haloalkanoic acid, or substituted haloalkanoic acid, with the formula

X-(CR'R' ' JnCOOR_i, wherein R_l7 R' , R' ' and n have the corre¬ sponding meanings as for the quaternary ammonium compounds defined in claim 1 and X is a halogen which reactions have been carried out in a solvent selected from the group lower alcohols, glycols, polyglycols and glycol ethers, or in an inert solvent.

11. A reaction mixture product according to claim 10, characterized in that the solvent is ethanol or isopropan¬ ol.

12. Use of tertiary amines and quaternary ammonium compounds as defined in claim 1 as bactericides or con¬ ditioning agents.

13. Use of tertiary amines and quaternary ammonium compounds as defined in claim 1 as textile softeners.

14. Use of a reaction mixture product as defined in claim 10 or 11 as textile softener.

15. Compositions containing water and/or solvent, characterized in that they as active substance contain a tertiary amine or a quaternary ammonium compound having the general formulae

), respectively, wherein R are straight or branched alkyl or alkenyl groups with 7 to 24 carbon atoms, R_]_ is an alkyl group with 1 to 4 carbon atoms, n is an integer of 1 to 4 and R' and R' ' independent of each other are hydrogen, alkyl- or hydroxy¬ alkyl groups with 1 to 3 carbon atoms or hydroxyl groups, m is 0 or 1 and A is a group containing an ester group or a group containing an amido function and is a group 1) -(0-CH₂-CHR' ' ' )_p-0-C(0)-(CH₂)_q-

2) -C(0)O-CHR' ' '-CH₂-(O-CHR' ' '-CH₂)p-

3) -(0-CH₂-CHR' ' ' )_p-0-C(0)-O-CHR' ' '-CH₂-(O-CHR' ' '-CH₂)_p-

4) -C(0)-0-CH₂-C(OH)H-CH₂- or

5) -C(0)-NH-(CH₂)_z- wherein R' ' ' is hydrogen or a methyl group, p is 0 to 5, q is 1 or 2 and z is 2 or 3, whereby, however, the total number of alkyleneoxide groups in groups of type 3 does not exceed 5, R₂ is an alkyl or hydroxyalkyl group with 1 to 4 carbon atoms and X is an anion.

16. Compositions containing water and/or solvent, characterized in that they as active substance contain a reaction mixture product which is the product of a quater¬ nization reaction of tertiary amines as defined in claim l with conventional quaternizing agents or, alternatively, the reaction product of tertiary amines with the formula [R-(A)_m]₂NR₂, wherein R, A, m and R₂ are as defined in claim 1, and an alkyl ester of a haloalkanoic acid, or substituted haloalkanoic acid, with the formula X- (CR'R¹ ' )_nCOORι, wherein R_]_, R¹, R^! ' and n have the corre¬ sponding meanings as for the quaternary ammonium compounds defined in claim 1 and X is a halogen which reactions have been carried out in a solvent selected from the group lower alcohols, glycols, polyglycols and glycol ethers, or in an inert solvent.

17. Compositions containing water or water and solvent according to claim 15 or 16, characterized in that the pH of the compositions does not exceed 4.5.

18. Compositions according to claim 17, characterized in that the pH is within the range of from 2.0 to 4.5.