NL8101586A - QUATERARY AMMONIUM COMPOUNDS AND THE USE OF THESE COMPOUNDS AS A FLOCULATOR. - Google Patents

Description

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Ammonium ammonium compounds and the use of these compounds as a flocculating agent.

The invention relates to compounds with a number of quaternary ammonium groups, the preparation and use of these compounds as an onion flocculant and emulsifiers.

German Offenlegungsschrift 1 795 392 discloses the preparation of bifunctional compounds of the formula 1, in which Hal represents a chlorine or brine atom (preferably a chlorine atom) and the other substituents have the meanings indicated in claim 1. The aforementioned compounds of the formula I are used in accordance with the aforementioned Offenlegungsschrift used cross-linked polyamide amines by preparing reaction with secondary amines.

It has now been found that compounds of the aforementioned formula A as well as the hydrolysis products and reaction products thereof with non-polymeric mono- and / or bi-functional amines are valuable flocculants and demulsifiers for the separation of oil in water, respectively. water in oil emulsions. Although reaction products of A with primary or secondary lower alkyl amines are known, such reaction products with other amines are new.

The invention therefore relates to the flocculants and emulsion breaking agents mentioned in claims 1 and 2 as well as to the new compounds indicated in more detail in claim 3, which can be used for the stated purpose. Finally, the invention is also directed to a flocculation and demulsification process using the agents of claims 1 and 2 or the compounds of claim 3.

Preferred compounds according to claim 3 are those of formula 2a, wherein the X 'group is a group having 8101586 - 2 - ft * formula 7 of claim 1 "especially those in which none of the groups R represent a hydrogen atom or those in which at least one R substituent is an alkyl group of 8-18 carbon atoms.

Furthermore, those compounds are recommended in which both X1-5 substituents are equal. If in the new compounds k is> 0, ie if two or more C groups in the mol 1? are present, of course, may or may not be the same, preferably being the same. The same applies to k> 1 if 2 or more B groups are present in the molecule; However, it is also recommended here that both be the same.

According to German Offenlegungsschrift 1 795 392, compounds of formula 1 are prepared by reacting an excess of epi-halohydrin (in particular epichlorohydrin) with a monofunctional, secondary amine (especially dimethylamine) or a bifunctional tertiary amine (for example tetramethylethyl (lene-methylene) or mixtures thereof), which reaction takes place in an acid medium, that is to say the amine is at least partly in salt form Compounds of formula I which are preferred are those in which R 1 and R 1 represent a methyl group , x = 0 or 1, preferably 1 and Y represents the 2-hydroxy-1,3-propylene group.

These compounds of formula 1 are hereinafter referred to as "coupling component". Both of the reactive halogen atoms thereof may, as is known, be hydrolyzed or react with monofunctional, primary or secondary, lower alkyl amines to give terminal amines (or their salts). The agents of the invention may contain or consist of these known compounds, ie their active ingredient may be a compound of formula 2b, wherein C, A and m have the meanings indicated above and each X "(independently) a chlorine or bromine atom or a group of formula 2d, wherein R 1 is a hydrogen atom or an alkyl group of 1-¾ carbon atoms and also an alkyl group of 1-¾ carbon atoms.

81 01 586 t 9 - 3 -

Under alkaline conditions, the amine salts can be converted to the free form, and Formula 2b includes as many the salts as the free amines.

It is further known that the above-mentioned "coupling components" in the reaction with an excess of a di-primary amine (e.g. diethylene triamine) lead to compounds O of formula 2c, wherein C, D, k, A and i are the above p have given meanings. The compounds of the formula IIc are also suitable agents according to the invention.

The "coupling component" can also be reacted with ammonia, mono- or bi-functional amines, for which preference may be given to mono-functional tertiary amines of the formula (also those compounds in which R does not represent a hydrogen atom). The R groups are preferably α 3 £ 3 l l C2 ^ of C2 C2 g C2 hydroxy hydroxy alk alk alk alk alk groepen groepen groepen groepen groepen. Primaire primaire Verder primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire. Primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire primaire

Preferred tertiary amines are those in which all three R substituents represent hydroxyalkyl groups having 2-U 2 O carbon atoms, in particular the hydroxyethyl group, or one of the R substituents represents an alkyl group having 8 to 18 carbon atoms, in the especially an alkyl group with 10-1U carbon atoms, and the other two substituents are an alkyl group with It / mh carbon atoms, in particular the methyl or a hydroxy group alkyl group with 2 to H carbon atoms, in particular the hydroxyethyl group. Preferred primary or secondary amines for the reaction with the coupling components are those in which the R substituents, which do not represent hydrogen, are preferably alkyl groups with up to 20 carbon atoms, hydroxyalkyl groups with 2-6 carbon atoms or benzyl groups to be. Especially recommended primary and secondary amines are long chain alkyl amines with at least one alkyl group of 8-18 carbon atoms, such as coconut amine and tallow amine.

The reaction with monofunctional, tertiary amines results in quaternary ammonium compounds (on each.

8101586 *> * - Η - place of the molecule where the reaction takes place), due to which the further reactivity ends. Monofunctional tertiary amines can therefore be regarded as end groups, respectively. should therefore conclude the reaction series. Also in the reaction with ammonia or monofunctional, primary or secondary amines, the further reaction is excluded by the occurring salt formation, or that a neutralization with bromine takes place. On the other hand, in the case of bifunctional amines, the ratio of the reaction components to one another can control whether free amino groups or halogen groups are present at the molecular ends, which can then react further. A bifunctional amine can therefore be regarded as a bridge for a possible molecule enlargement.

An amine within the meaning of the present invention 15? can then be considered bi-functional if it contains two reactive amino groups that readily react with the coupling component; those amines are also bi-functional, which additionally contain less reactive amino groups, i.e. those which react more difficult. Such a bifunctional amine is, for example, diethylene triamine (Η2Ν-02Η ^ -Η-02Η ^ -Μ2). Preferred groups B are those aforementioned groups of formula 3 wherein R 1, independently of one another, is a hydrogen atom or a methyl group and D is an alkylene group having 2 to 12 carbon atoms, preferably -CgH 2 -, - (CH 2 Jg- or 25 - (CH2) 12 ~ or a group of formula 5, wherein e = 1, d and f, independently of each other, 2 or 3 and Rg represent a hydrogen atom. B may also be a group of formula 6, wherein D 'forms a piperazine ring with the nitrogen atoms and each p = 1, R' = H and q = 0.

Preferred other classes of groups B are those of formula 3, wherein three R 1 substituents represent a hydrogen atom and one R 1 substituent is an alkyl group having 8 to 20 carbon atoms, especially an alkyl group having 11-15 carbon atoms.

For example, two moles of coupling 8101586% 4 è - 5 -

coranonent Cl-C -Cl first with 1 mol of a diamine of formula P.

(Rf] ^ N-D-1CR ') 2 to a compound of formula 9 and this

further with 2 moles of a monofunctional amine of formula (Ri ^ N

react at the ends to form a compound of formula 10.

To increase the ratio of the bi-functional amine to the coupling component in the first step, the number of units can be increased, as will be appreciated, to yield a linear polymeric compound in equimolar amounts.

When the amine component is further increased, compounds 10 form terminal amino groups and compounds of formula 11 are formed at a ratio of the bifunctional amine to the coupling component of 2: 1. Such compounds can now be exchanged with another coupling component Cl-C'-Cl

P

and then be converted again with a tertiary amine to compounds of the formula 12. Thus, such a stepwise construction allows a multitude of different, linear structures to be obtained.

It will be understood that if one or both R * substituents are hydrogen atoms, the cationic group% 20 -N (R ') 2 is an amine salt and not a quaternary ammonium salt.

Neutralization produces secondary amines (-ΓΤΗ-) or tertiary amines (-NR'-) under deprotonation. The basicity and water solubility of such a compound obviously differs from that of the salt. The same considerations apply to the end groups (R) ^ TT-, if one or a number of R substituents represent hydrogen atoms.

The special properties of the compounds of the invention or the agents of the invention depend on the chain length molecule, the spacing of the quaternary groups in the chains and the nature of the side chains or side groups. In the normal water-soluble compounds, for example, by incorporating many lipophilic side chains, these can be changed to water-insoluble compounds.

The anion A will usually be the anion of the acid used for the preparation of the coupling component, as well as the halogen anion from the epihalohydrin used. When HCl and epichlorohydrin are used, 9 q, therefore, all A anions are chloro anion Cl. Naturally, the anions in the end products can be exchanged in a known manner.

It also goes without saying that with a poly-ΘΘ θ ΘΘ valentanion, for example SO ^, the symbol A 1/2 represents SO ^.

Mixtures of compounds of the formula II can be obtained by using mixtures of starting materials or intermediates (in step-wise construction).

The coupling components themselves or the end products with terminal halogen groups (for example of formula 9) can be hydrolyzed (with aqueous alkalis) to thereby give compounds with terminal hydroxyl groups.

The reaction conditions for the preparation of the compounds according to the invention or the compounds to be used according to the invention depend both on the desired end product and on the properties of the starting materials or on the stepwise construction of those of the intermediates. In the case of reactive amines, the reaction generally proceeds exothermically, also when the coupling component is present in aqueous solution. In that case it will be possible to control the reaction by slowly adding a reaction partner, whereby the reaction can sometimes be kept under control by additional cooling. The initial temperatures are usually between 0 and 100 ° C, preferably between 20 and 60 ° C. The upper temperature limit is mainly determined by the boiling point of the amine used, as well as the desired end product. In some cases, one or the other reaction component and also both may be present in an aqueous solution or react in the presence of water, which may also be present in the preparation thereof. In other cases, the absence of water will be an advantage or necessary and, if desired, the reaction can also take place in polar or non-polar organic solvents.

81 01 586 *? - 7 -

Amines with a low reactivity or low water solubility during the reaction require special reaction conditions and, if possible, careful control of the pH. A polar solvent is usually advantageous or necessary for a homogeneous distribution in the reaction medium.

It will normally be advantageous to mix the reaction components at room temperature and to start the reaction by raising the temperature. The reaction temperature will generally be higher than with more reactive amines, and the reaction often does not proceed exothermically. Naturally, the selection of the most suitable solvent will also be influenced by the aforementioned factors. Its boiling point is above the reaction temperature. The type of solvent often also influences the nature of the end product and the choice of the most suitable solvent in each case is therefore also influenced by this.

The reaction temperatures in such cases are usually above 60 ° C (up to 100 ° C). Suitable are, for example, low alcohols, for example ethanol and n- and iso-propanol and glycols, such as ethylene glycol or its ethers. The solvent can optionally be distilled off or left behind in the reaction medium in a stepwise build-up and sometimes even form a component of the final product. If the amine is sparingly soluble in water or is slightly reactive, it can be an advantage if the coupling component contains little or no water.

The course of the reaction can be checked, for example, by measuring the consumption of the amine (or the coupling component) or in the step-by-step build-up of the intermediates, or also by measuring the ion formation, for example from the α-chloro-0-hydroxyethyl group of the coupling-20 component, by determination of the chlorine ions. The reaction is then ended when the theoretical amount of Cl9 ions has been formed and also if the concentration thereof remains constant after a certain time.

The hydrolysis of the halogen end group (up to 25 hydroxyl) can for instance take place in a dilute solution of sodium 8101586-8-hydroxide in water at a temperature of about 60 ° C.

The compounds of formulas 1, 2 and 2a have a surface active action, which means that they can be used as a flocculating agent and also as an emulsion breaking agent. Oil-in-water as well as water-in-oil emulsions can be effectively separated using the compositions of the invention. Flocculation within the meaning of the present invention means the initial stage of de-emulsification. In oil-in-10 water emulsions, flakes form separate oil droplets, which further coagulate into larger aggregates. If the breaking of the emulsions does not go beyond this stage, ie the "flakes" do not completely separate, they usually still contain so much water that they do not qualify for incineration or further processing without additional treatment.

For the most part, the agents according to the invention process in a second phase the entire association of the "flakes" into an oil layer, which contains practically no water. This 20 step, the transition from "flocculation" to a separate oil phase, can be promoted by heating.

In the examples below, the parts are parts by weight or by volume. Percentages are weight percentages and temperatures are given in ° C.

Example I;

To a mixture of 351U parts of water (demineralized) and 1131 parts (2 mol) of a 60% dimethyl amine solution, 803 parts of 30% HCl were slowly added (temperature: 35 DEG-0 DEG C.). 2093 parts of 30 (3 moles) of epichlorohydrin were added with cooling and continuous stirring at such a rate that the temperature was maintained at 35 DEG-0 ° C.

After the completion of the addition, the mixture was allowed to react for a further 8 hours at a temperature between 35 and 10 ° C and then cooled to 25 ° C. The 3: 2 adduct contained 2 moles of Cl0 and 2 moles of nonionically bound chlorine.

8101586 - 9 -

Example II

10K, 3 parts of 35% HCl (1 mol) was added slowly to 150 parts of a βθ% dimethylamine solution (2 mol) with cooling and stirring, keeping the temperature below 5 ° C. After cooling to 35 ° C, 277.5 parts (3 moles) of epichlorohydrin were added, adding at such a rate that the reaction temperature did not exceed 10 ° C. Finally, the mixture was stirred for an additional hour at 50 ° C and the reaction mixture was left overnight.

Example III

121.67 parts of 30% HCl (1 mol) was slowly added to 210 parts of diethanolamine (2 nol) (temperature <10 ° C). After the addition, 277.5 parts (3 moles) of epichlorohydrin were added at 35 ° C at a rate such that the reaction temperature did not exceed 1 + 0 ° C. Finally, the mixture was stirred for an additional 1 hour at 50 ° C and the reaction mixture was left overnight. Example IV

86.3 parts of 36.5% HCl (2 mol) was mixed with 110 parts of demineralized water at 15 ° C and then 20 were added with the addition of 50 parts (1 mol) of tetramethyl ethylene diamine, the temperature being between 35 and ^ 0 ° C.

After cooling to 25 ° C, 79.8 parts (2 mol) of epichlorohydrin was added (duration about 1 hour) and the temperature was kept at 25 ° C. Finally, the reaction mixture was kept at 25 ° C overnight.

Examples V-XX

In each of the following examples, 1 mole of the coupling component of said example was reacted with 2 moles of a monofunctional amine to yield compounds of formula R 1 -C - x 2 Cl® 3 p 3 q. The reaction was continued until the Cl content remained constant. Table A below lists the reaction constituents, conditions, etc. When additional solvent is added, the amount thereof is based on the amine (parts by weight: amine = 1).

81 01 586 »v - 10 -

Table A

pre-coupling additional dissolution reaction component amine R ^ N means of Example VX (CgH-Lflf ethanol reflux under 5 (3.7 parts) for 5 hours, then distill off the ethanol VI II (OV ^ Hn --- Flow back 8 hours, pH 7

by adding 30% AlOH

VII II Ν (σ2Η ^ 0Η) 3 - 85-95 ° / k hours VIII II HN (C2Hu0H) 2 --- 60-70 ° / k hours IX I (> ”2 65-75 ° / 3 hours XI ^ OVcHcNH0 - 6θ ° Λ hours, then V- / 2 2 80 ° / 1 hour; 90 ° / 2.5 hours, 90 ° / 3 hours XI II (nC.H) _N ethylene glycol- 85 ° / 20 hours y ° monoethyl ether (0 , 8 parts), ethanol (3.9 parts) XII II coconut fat di-110 ° / 20 hours The alkylamine product is waxy (R ') NH (sun) XIII I ethoxylated - 95/10 hours (the tallow fat amine product is a

RtN (C 2 H, 0H) 2 solid wax which is (z.o.7 soluble in ethanol) XIV I 60-70 ° / 3.5 hours XV I fat monoalkyl ethylene glycol 75 ° / 1 hour, amine R JTH. monoethyl ether then 90 ° / 2l hours (z.o.) r 2 (0.33 parts) XVI I fatty dialkyl- as for example

amine (R J0NH picture XV XV

(z.o.) f2 XVII I dimethylmono- --- 70 ° / 1 hour therefo fatty amine after 90/2 hours R N (CH_) 0 (z.o.) C 3d 81 01 586 t - 11 - 'f r

Table A (continued) pre-coupling additional dissolution reaction example component amine RJT means of Example XVIII III ΙΓ (σ2Η ^ 0Η) 3 - 85-95 ° / 4 hours XIX IV (CR «), N (27.5 # - 90 ° / 10 hours aqueous solution) 10 XX IV see example - 95 ° / 10 hours

XIII

The coconut fat alkyl group R has the tallow fat alkyl group R. (hardened) C u the following composition: has the following composition:

Caproyl (C6) 0.5 parts Myristyl (C14) 3.5 parts 15 Caprylyl (C8) 8.0 "Pentadecyl (C15) 0.5"

Capryl (C10) 7.0 "Palmityl (C16) 30.0"

Lauryl (C12) 50.0 ”Margaryl (C17) 1.5 M

ifyristyl (C14) 18.0 "Stearyl (C18) 62.5"

Palmityl (C16) 8.0 "Myristoleyl (Cl4) 0.5" 20 Stearyl (C18) 1.5 "Palmitoleyl (Cl6) 0.5"

Oleyl (C18) 6.0 "Oleyl (C18) 1.0"

Linoleyl (C18) 1.0 ”

The fatty alkyl group has the following composition: C13 alkyl 70 parts, C15 alkyl 30 parts, in which 50 parts are straight chain and 50 parts are branched (mainly 2-methyl).

Example XXI

The compound of Example I (aqueous preparation) (1 mole) was heated to 40 ° -50 ° C and then 174 parts (2 moles) of the following commercially available diamine mixture was added dropwise within 1.5 hours. 30-36% hexamethylene diamine and 64-70% diaminocyclohexane. This mixture was stirred at 50 ° C for 4 hours, after which, according to analysis, the theoretical amount of Cl was present. The product has the aforementioned formula XI.

Examples XXII - XXX

In each of these examples, 2 moles of 8101586 V t-12 - of the coupling component of Example I were reacted with 1 mole of the functional amine listed in Table B each time to give compounds of the type Cl - C - - B - - Cl .

Table B also mentions the reaction conditions.

Table B

for additional reaction conditions - bifunctional amine release agent present xxii h2nch2ch2nh2 --- 60 ° / 2 hours XXIII üw ^ kiü - ^ 0 ° / 2 hours, then é0 ° / 1 hour 85 ° / 2 hours, then 95 ° / 1 hour XXIV H NCH CHgCHgHH ^ - 6o ° / 2 hours XXV HJfiCHjJBL --- 60 ° / 1 hour, then 2 2 6 ^ 80 ° / h hours XXVI H0N (CH0), _ NH «--- 60 ° / 1 hour, then 2 2122 80 ° / k hours y— \ XXVII HN N-CH_CH0liH- --- 85 / H hours

(L £ iL

XXVIII H_NCH_CH0NHCH_CH-NH0 --- Uo ° / k hours, then 222 222 6o ° / 2 hours XXIX R NHCH CH CH-NH industry- 85-90 ° / 18 hours v + ,, t \ alcohols (^ -kosvetakjrl) ( , dMl) _ VZ.O.) XXX | \ | (Sj 1, h-diazabi-50 ° / 1 hour, then ^ / cyclo-octane 90 ° / 2 hours

Examples XXXI - XLI

In each of the following examples, 1 mole of a compound of Examples XXII-XXX was further reacted with 2 moles of a monofunctional amine to give compounds of the type R 1 -C-B-B-x 2. The reaction components and reaction conditions are listed in the following Table C.

8101586

- 13 - Table C

bridging part additional dissolution reaction image of amine R_N agents image -3 ___ XXXI XXII N (C 1 -CH 2 OH) 3 - 85-95 ° / h hours XXXII XXIII n (CH 2 CH 2 OH) 3. --- 95-98 ° / 3 hours XXXIII XXII HN (CH2CH20H) 2 --- 60-70 ° / 1 »hours XXXIV XXV (CHyYYH (60% --- b0 ° / 3 hours, then aqueous op- 70 / 1 hour discharge) XXXV XXV as in example XIII - 5CT / 1 hour, 80/7 hours XXXVI XXV - 60-70 ° / 3.5 hours XXXVII XXVI (CH-LNH (60jf - k (P / 3 hours, then 3 f 70 ° / 1 hour aqueous solution) XXXVIII XXVI --- 6θ ° hours, then 2 80 ° / 1 hour 90 ° / 2.5 hours, 95 ° / 3 hours XXXIX XXVI NiCHgCHgOH ^ - 85 ^ 5 ° / hours XL XXX N (CH2CH20H) 3 --- 95 ° / 16 hours XLI XXX (R.) n (CH,) isonropanol 90-95 ° / 16 hours (R «fatty alkyl (^ 7 parts) + r «VetaiKyi, ethylene glycol _z, ö,) _ (4.7 parts) _

Example XLII

Oil-contaminated industrial wastewater, containing about h% of oils and fats and contaminated with other industrial waste, was treated with various flocculants. The fat-contaminated wastewater used in this example contained a mixture of mineral oils and grease residues from the metal industry. Non-ionic surfactants (polyethylene glycols, ethoxylated higher alcohols or phenols) had only limited activity in large amounts. Aluminum chloride caused flocculation at 2000-5000 ppm, but water was also included, and the aqueous phase was still cloudy. In a smaller amount of 8101586-1 clan 1000 ppm, aluminum chloride was ineffective, as was calcium chloride and ferric chloride.

The product of Example VII already produces at 200 ppm. flocculation and phase separation take place within 5 2b hours. The (top) oil layer was homogeneous and the (bottom) water layer was clear and colorless.

Example XLIII

Here, the oily contamination (*, b%) was a mixture of animal fat and mineral oil as the main constituent and small amounts of esters of fatty acids and higher alcohols, fat additives, emulsifiers and industrial wastewater, also from the metal industry.

Inorganic flocculants hardly have any effect. The product of Example VIII was 15 at 10,000 ppm, that of Example VII at 5000 ppm. and that of Example XXXI at 1000 ppm fully active and cause slow phase separation, which ended within 2-3 days, leading to a homogeneous oil layer and a transparent light colored water layer.

Example XLIV

Wastewater from the steel industry, containing 1.03% aqueous phase roll oil, was treated by the following means of the invention: a) The products of Examples XIII, XVII, and XIX were active in an amount between 1000 and 5000 ppm.

A flocculated oil layer and a slightly cloudy water phase were obtained; b) the products of Examples XL and XLI gave in an amount between 1000 and 5000 ppm. a rather cloudy water phase and an almost completely anhydrous oil layer; c) the products of examples XVI, XXXIV, XXXVII and xxxvill were active in an amount between 500 and 1000 ppm, the image obtained was the same as under a); d) the product of Example XV was active in an amount between 500 and 750 ppm. The water phase here was 8101586-15 - clearly clearer than it a). To 1U 000 1 of the aforementioned waste water in a tank was added 750 ppm. of the product of Example XV. The contents of the tank were mixed well by circulating (for 6 minutes), after which it was left to stand at 28 ° C for 0 hours. The water layer then contained only 0.06% oil-containing constituents. The flocculated top layer was heated to 60 ° C after separation and after 1 hour contained only 1.3% water.

Example XLV

A bitumen processing equipment (oxidative processing) gave a distillate consisting of ~ 60% water and ~% oil (water-in-oil mixture). The products of Examples V, XIII, XIV and XIX were effective in an amount between 1000 and 2000 ppm. and phase separation with a clear, slightly brownish, water phase. The separation took place more quickly at U0-U5 ° C (the temperature of the distillate) and could be improved even further by increasing the temperature.

29,000 L of the above-described water-in-oil emulsion with a water content of 62 tk% (pH 9.6) at 50 ° C was added at 1000 ppm. of the product of Example XIII.

The pH was adjusted to 7 with ICI. Good mixing was achieved by pumping for 30 minutes. Phase separation started immediately and ended after 15 hours.

An oil layer containing no water and a clear, aqueous phase was obtained, the latter phase suitable for being fed into the public waste water.

8101586

Claims (6)

1, Method for preparing a flocculation resp. emulsion-breaking agent, characterized in that an agent is prepared which consists of one or more compounds of the formula 1, in which Hal is a chlorine or bromine atom, preferably a chlorine atom, and Rg, independently of each other, an alkyl group with at most 5 carbon atoms or a hydroxyalkyl group with 2-5 carbon atoms and Y an alkyl group with 2 to 6 carbon atoms, a 2-hydroxy-1,3-propylene group or a 10 -CgH ^ -NH-CO-NH-CgH ^ - or -C 4 gM-CO-NH-4 Hg group, as well as the hydrolysis products and reaction products with ammonia and / or non-polymeric mono- and / or bi-functional amines thereof and x is an integer from 0-7 if x is greater than ► 2, each of the symbols Y need not be the same, exists 15 or contains. 2. Process according to claim 1, characterized in that an agent consisting of or containing a compound of formula 2 is prepared, in which C is a group of formula 1 P without Hal, B represents a group of formula 3, in which the substituents R ', which may or may not be the same, represent a hydrogen atom, an alkyl group of 1-20 carbon atoms, an alkenyl group of 2-20 carbon atoms, a hydroxyalkyl group of 2-6 carbon atoms, an aralkyl group or a group of formula U, wherein a hydrogen atom or a methyl group can be 25 and n is a number, from 2-150, preferably 2-50, and the substituents R1 can be the same or different, D an alkylene group with 2-20 carbon atoms or a group with formula 5, wherein e is a number from 1 to 5, d and f, independently of each other, are numbers from 2 to 5 and Rg is a hydrogen atom, an alkyl group of at most 6 carbon atoms, a hydroxyalkyl group of 2 to 6 carbon atoms, or a haloalkyl group with at most 6 carbon atoms one or a radical of formula f can be R ^ (CH2 ^, where g and h, independently of each other, are numbers from 0-3 and R ^ represents a 5-7 ring, - 35 being wholly or partially unsaturated and which may be carbocyclic 8101586 * - 17 - or an oxygen and / or nitrogen-containing heterocyclic ring, or wherein B represents a group of formula 6 wherein D 'together with the two nitrogen atoms selected one or more ring systems selected from 5- 7 forms rings which may or may not be saturated or aromatic and may contain further nitrogen atoms, R 'and d have the meanings indicated above and p and q, independently of each other, may be 0 or 1, each X independent of each other chlorine, bromine, hydroxyl or a group of formula 7, wherein the substituents R, which may or may not be equal to 10, are a hydrogen atom, an alkyl group with at most 20 carbon atoms, an alkenyl group with 2-20 carbon atoms, a hydroxyalkyl group with 2-6 carbon atoms, a cycloalkyl group with 3-8 carbon atoms, a phenyl group, an aralkyl or alkaryl group, or a group of the formula U, or wherein both 15 R substituents, together with the nitrogen atom to which they are attached, form an unsaturated 5-7 ring, which may contain one or more oxygen or further nitrogen atoms as well as have alkyl substituents in places not adjacent to nitrogen atomic atoms, or wherein three substituents R together with the nitrogen atom to which they are attached form a polycyclic ring, which further oxygen or may contain nitrogen atoms, or form a heterocyclic-aromatic ring system containing one or more additional nitrogen atoms, a group of formula 8 wherein R 1 and D have the meanings indicated above and k a number, preferably of 0- 5, in particular 0 or 1, and A is an anion, where m is a number equal to the number of cationic sites in the molecule. 3. Compounds of formula 2a, in which Θ C, B, k, A and m have the meanings P ^, X 'has the meaning of X, with the following limitations in case k * ao) X' cannot be chlorine or bromine, b ) if each X in the total molecule is a group 35 having the formula 7 indicated in claim 1, then if 8101586 '4 *> - 18 - two substituents R in each of the X groups are alkyl groups having 1-U carbon atoms, at least one of the other two R groups in the total molecule and if one substituent R in each of the X groups is an alkyl group with 1-U carbon atoms, at least one of the four other R substituents in the total molecule is different from hydrogen, and c) if each X substituent is a group of formula 8 of claim 1, at least one R 'substituent is different from hydrogen. U. A process for flocculation or de-emulsification, characterized in that an agent according to claims 1 and / or 2 or one or more compounds according to claim 3 is used for this. 5. Methods as described in description 15 and / or examples. f ^ 81015 8 6 R, Ri u i 'pu ru ru, n__Y - N CH * —CH —CH * -Hal Hal — CHa - CH - Νφ j® j OH Rz. x 0H ^ x-Cp-B— c ^ - x [a®] ^ x4Cp_BiCP x 1-A 2a Jk £ R \ © [a®]. 2b 2d Η, ΙΙ-0 Λπ, -ίΐ, - ^ ", - D-®IHtl · C, -V-" - [* °] »/ <2C r 'R Γ _A®_D_ CH CH 0 - H k R '3 L Rr J »4 ~' (CHz) d-NR4— (CH?) f— 5 (R '} p ^ _. (R') pff —— N θ'N --'_" ( CH4? © c ® © d J, 6 R * R 'RN— N —O —N- /, B · / L ft k .7 RR ° R' r 'qf'. "9 - *" θ 10 k ' 1 / \ "* 1 R 1 \ _0 flLcp - ^ - o —N \ p 'x2ClS 11 8101586 RR — N-Cp-i® o —I-Cp - ^ - 0 -N —Cp-N ^ -R« SCI0 ^ RX R 'R' R '. R' R * "_______ ·. __% j-.uί ~> - <λ