DE3111386A1 - "QUATERNAIRE AMMONIUM COMPOUNDS AND THE USE THEREOF AS A FLOCULATING AGENT" - Google Patents

Description

The present invention relates to compounds having a plurality of quaternary ammonium groups, their production and use as flocculating agents and de-emulsifiers.

DE-OS 17 95 392 describes the production of bifunctional compounds of the following formula (I) known

OH

Hal -CH ₀ -CH-CH _n -R ₇ Cf γ-wf (M -CH-CH ..- Hal

I,

OH

in which Hai stands for chlorine or bromine (preferably chlorine) and the further radicals have the meaning given in formula I of claim 1. The aforementioned compounds (I) are according to the information in "DE-OS 17 95 392 used to produce crosslinked polyamide amines by reaction with secondary amines.

It has now been found that compounds of the type of the aforementioned formula A as well as their hydrolysis products and reaction products with non-polymeric Mono- and / or bi-functional amines valuable flocculants and de-emulsifiers for the separation of oil-in-water and water-in-oil Are emulsions. While reaction products of A with primary or secondary lower alkylamines are known, such reaction products are new with other amines.

The subject matter of the present application are therefore those in claims 1 and 2 mentioned flocculant and emulsion-breaking agents as well as the iin claim 3 new compounds which are specified in more detail and which can be used for the stated purpose. The subject of the present application is and finally a flocculation and de-emulsion process Use of the agents according to Claims 1 and 2 or of the compounds according to Claim 3.

Preferred compounds of claim 3 are those of the formula Ha, in which the group X ^{1 is} one of the formula VII of claim 1,

- 6 - Case 370-3710 F / C

especially those in which none of the groups R is hydrogen or those in which at least one R is a C ₀ , _o -alkyl group. Loading

O "Io

Also preferred are those compounds in which both X 'are the same.

If in the n & uen compounds k> -0, i.e. two or more C groups are present in the molecule, these can of course be the same or different from one another, preferably they are the same. The same applies when k> −1, if 2 or more B groups are present in the molecule, preferred are both the same here as well.

According to DE-OS 17 95 392, compounds of the formula I are prepared by reaction of an excess of epi-halohydrin (especially epichlorohydrin) with a monofunctional secondary amine (especially dimethylamine) or a bifunctional tertiary amine (e.g. tetramethylethylenediamine (or mixtures thereof), this reaction taking place in an acidic medium, i.e. that the amine is at least partially in salt form is present. Preferred compounds of the formula I are those in which R 1 and R 1 are methyl, x = 0 or 1, preferably 1 and Y is the 2-hydroxy-1,3-propylene group is.

These compounds of the formula I are hereinafter referred to as "coupling component" designated. Your two reactive halogen atoms can be hydrolyzed as known or with monofunctional primary or secondary lower alkylamines react, whereby terminal amines (resp. their salts) arise. The agents according to the invention can use these known ones Contain or consist of compounds, i.e. the active ingredient can be one of the formula Hb.

X "- C - X" [Α ^Θ ] Hb,

ρ m

where C, A and m have the meanings given above and each X "(independently from each other) fin chlorine, bromine or the group

can be in which R is hydrogen or C ₁ .Alkyl and R is C ₁ .Alkyl.

3 1-4 4 -1-4 ^J

· '■ * "" - 3111336

- 7 - Case 370-3710 F / C

Under alkaline conditions, the amine salts can go into their free form be transferred, and the formula Hb is intended to include both the salts and the free Include amines.

It is also known that the "coupling component" referred to above when reacting with an excess of a di-primary amine (e.g. diethylenetriamine) leads to compounds of the formula lic.

H ₂ ND-NH ₂ + C ^ -NH ₂ -D-NH ₂ ^ - _k C-NH ₂ -D-NH ₂ [Α ^θ ^ Hc, where C, D, k, A and m have the meanings given above . The compounds of the Hc type are also suitable agents according to the invention.

The “coupling component” can also be reacted with ammonia, monofunctional or bi-functional amines, monofunctional tertiary amines of the formula RN (ie those in which R sees hydrogen) being preferred. The R groups are preferred: C _n -alkyl or C_, -hydroxyalkyl radicals. Primary, secondary or tertiary amines with at least one C 6 alkyl group are further preferred.

8-18

Preferred tertiary amines are those in which all three radicals are RCr Hydroxylalkyl, especially the hydroxyethyl radicals or one of the groups R

C-alkyl, especially C- _n -alkyl, and the other two C -alkyl, o ~ Io 10- Xh · L 4

especially methyl or C1, -hydroxylalkyl, especially hydroxyethyl, are.

Preferred primary or secondary amines for the reaction with the "coupling component" are those in which the R groups, which is not preferable are hydrogen C, _2 ~ ₀ alkyl, C2_g-hydroxyalkyl or benzyl radicals. Particularly preferred primary and secondary amines are long-chain alkylamines with at least one C ₀ , "- alkyl group, such as coco-amine

o-Xo

or sebum amines.

In the reaction with monofunctional tertiary amines, quaternary amines are formed Ammonium compounds (at each point of the molecule where the reaction takes place), whose further reactivity then ceases. Monofunctional tertiary amines are therefore to be regarded as end groups or they serve to complete the reaction sequence. Even with the

- 8 - Case 370-3710 F / C

Reaction with ammonia or monofunctional primary or secondary Amines are precluded from further reaction due to the salt formation that has taken place, unless neutralization with bromine takes place. On the other hand In the case of bifunctional amines, the ratio of the reactants to one another can be used to control whether there are any Free amino groups or halogen groups are located, which can then each react further. A bifunctional amine can therefore act as a bridge member for a possible molecular enlargement.

For the purposes of the present invention, an amine is to be regarded as "bifunctional ¹¹ " if it contains two reactive amino groups which react easily with the "coupling component"; amines are also "bifunctional" which additionally contain less reactive amino groups, ie those which Such a "bifunctional" amine is, for example, diethylenetriamine (H NC ₀ E -NH-C H-NH).

Preferred groups B are those of the abovementioned groups of the formula III, in which R ^1, independently of one another, is hydrogen or methyl

and D is a C ₀ "alkylene radical, preferably -C ₀ H.-, - (CH ₀ ) - or - (CH ₀ ). z—J./ δη / o L IZ

or a group of the F.irmel V, in which e = 1, d and f are independently 2 or 3 and IL-hydrogen. B can also be a group of the formula VI in which D ¹ forms a piperazine ring with the nitrogen, each p = 1, R '= H and q = 0.

Further preferred classes of groups B are those of the formula III in which three R ^{1 are} hydrogen and one group R ^{1 is} a C alkyl, especially a C alkyl group.

For example, two moles of the "coupling component" Cl-C-Cl can only be ^{reacted with one mole of a diamine (R ') NDN (R 1} ) to form a compound of the formula IX.

R ¹ R ¹

Cl-C-N-D-N-C-Cl x 2 Cl

Pi ι Ρ
R 'R ¹

'"' J" 11386

- 9 - Case 370-3710 F / C

and this further end-capped with 2 moles of a monofunctional amine (R) N become a compound of formula X

R ^ ffi

RNC -TJ-D -N -CNR χ 4 Cl R ^P 'ι Ρ \ _R
^R R 'R' ^R

When increasing the ratio of the bifunctional amine to the "coupling component" In the first step, as can be seen, the number of units can be increased, a linear polymer with equimolar amounts Connection is established. If the amine component is increased further, arise Compounds with terminal amino groups and a ratio of bifunctional amine to "coupling component" of 2: 1 are formed Compounds of Formula XI

N - D - N - C - & - J) - N ^ χ 2 Cl XI ^R R 'R « ^R

Such compounds can now be ^{reacted with another "coupling component" Cl-C 1} -Cl and then end-capped with a tertiary amine to give compounds of the formula XII
R ¹ R 'R' R '

R-N-C-N-D-N-C -ίί -D-N -C-N- R X 6 Cl XII

_R / P t, P,, P \ _R

^K R ¹ R ¹ R ¹ R '

With such a step-by-step structure, a large number of different linear structures can be obtained.

It can be seen that when one or both of R ^{1 are} hydrogen, the -N (R ¹ ) cationic group is an amine salt and not a quaternary ammonium salt. During the neutralization, secondary amines (-NH-) or tertiary amines (-NR ¹ -) are obtained with deprotonation. The basicity and the water solubility of such a compound is of course different from that of the salt. The same considerations apply to the end groups (R) N- when one or more R are hydrogen.

- 10 - Case 370-3710 F / C

The special properties of the compounds according to the invention or Means depend on the chain length of the molecules, their distance between the quaternary groups in the chains and the nature of the side chains or Subgroups. In the case of the normally water-soluble compounds, e.g. through the incorporation of many lipophilic side chains, these up to Water insolubility can be changed.

The anion A will usually be that of the acid that is responsible for the Preparation of the "coupling component" was used as well as that halogen anion from the epihalohydrin used. When using HCl

Θ Θ

and epichlorohydrin are therefore all A is the chlorine anion Cl. Of course the anions in the end products can be exchanged in a known manner.

Of course, in the case of a polyvalent anion, for example SO, the symbol A stands for 1/2 SO ₄ .

Mixtures of the compounds of the formula II can be obtained by using Mixtures of starting materials or intermediate products (in the case of stepwise Structure).

The "coupling component" itself or such end products with terminal Halogen residues (e.g. of the formula IX) can be hydrolyzed (with aqueous alkali) and produce compounds with terminal OH groups.

The reaction conditions for the preparation of the compounds according to the invention or to be used according to the invention depend both on the desired end product and on the properties of the starting materials or, in the case of a step-by-step structure, on those of the intermediates. In the case of reactive amines, the reaction is generally exothermic, even if the “coupling component” is in an aqueous solution. In this case it will be possible to control the reaction by slowly adding a reactant, the reaction possibly having to be kept under control by additional cooling. The initial temperatures are usually between 0 and 100 ⁰ C, preferably at 20-60 ⁰ C. The upper temperature limit is largely determined by the boiling point of the used

- 11 - Case 370-3710 F / C

Amine as well as according to the desired end product. In certain cases like one or the other reaction component or both are present in aqueous solution or are reacted in the presence of water, which can also be present from the production of the same. In other cases the absence of water is beneficial or necessary and, if appropriate, the reaction can also take place in polar or non-polar organic solvents.

Amines with low reactivity or low water solubility require special reaction conditions and possibly careful control of the pE value during the reaction. A polar solvent is usually advantageous or necessary for homogeneous distribution in the reaction medium. It may normally be convenient to mix the reaction components at room temperature and start the reaction by increasing the temperature. The reaction temperature will generally be higher than with more reactive amines and the reaction is often not exothermic. The choice of the most suitable solvent will of course also be influenced by the factors mentioned above; 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 is therefore also influenced by this. The reaction temperatures are in such cases usually above oO ° C (up to 100 ⁰ C). Lower alcohols such as ethanol and n ~ and iso-propanol and glycols such as ethylene glycol or their ether are suitable

form.

If the amine is poorly water-soluble or inert, it can be advantageous that the "coupling component" is largely or completely anhydrous.

The reaction process can be monitored, for example, by measuring the consumption of the amine (or the "coupling component") or in the case of a gradual build-up of the intermediate component or by measuring the ion formation

- 12 - Case 370-3710 F / C

formation, e.g. from the α-chloro-ß-hydroxyethyl group of the "coupling component" by determining the chlorine ions. The reaction is ended when the theoretical amount of Cl ions has formed or also if their concentration remains constant after a certain time.

Hydrolysis of the halogen-terminated (to hydroxyl) can be carried out, for example, in dilute aqueous sodium hydroxide solution at temperatures of about 60 ⁰ C.

The compounds of the formulas I, II and HA have surface-active substances Effect due to which they act as a flocculant or as an emulsion-breaking agent Funds can be used. Oil-in-water as well

Water-in-oil emulsions can be obtained by means of the preparations according to the invention be effectively separated. For the purposes of the present invention, flocculation means the initial stage of de-emulsification. With oil-in-water emulsions, flakes form individual oil droplets which further coagulate to form larger aggregates. When breaking the Emulsions does not go beyond this stage, i.e. the "flakes" do not separate completely, then they usually still contain so much water that they are not suitable for incineration or further processing without additional treatment.

The agents according to the invention work for the most part in one second phase the complete union of the "flakes" to an oil layer that hardly contains any water. This process, namely the transition from "Flake" to a separate oil phase can be accelerated by heating.

In the following examples, parts are parts by weight or volume, Percent are percentages by weight and the temperatures are given in degrees Celsius.

example 1

A mixture of 3514 parts of water (demineralized) and 1131 parts (2 mol) of a 60% dimethylamine solution is slowly mixed with 803 parts of 30% HCl (temperature: 35-40 °). Be with cooling and constant stirring

- 13 - Case 370-3710 F / C

then 2093 parts (3 moles) of epichlorohydrin were added, with the temperature is kept at 35-40 ° '.

After the addition has ended, the reaction is left to complete for 8 hours at 35-40 ° and cools down to 25 °. The 3: 2 adduct contains 2 moles of Cl and 2 moles of non-ionically bound chlorine.

Example 2

104.3 parts of 35% HCl (1 mole) are slowly added to 150 parts of a 60% dimethylamine solution (2 mol) are added with cooling and stirring, the temperature being kept below 40 °. After cooling to 35 °, 277.5 Parts (3 mol) of epichlorohydrin are added, the addition being carried out in such a way that the reaction temperature does not rise above 40 °. It will be 1 hour at Stirred 50 ° and left to stand overnight.

Example 3

121.67 parts of 30% HCl (1 mole) slowly turns into 210 parts of diethanolamine (2 mol) added (temperature <40 °). After the addition is complete, 277.5 parts (3 mol) of epichlorohydrin are added at 35 ° so that the reaction temperature is reached does not rise above 40 °. The mixture is stirred at 50 ° for 1 hour and left to stand overnight.

Example 4

86.3 parts of 36.5% ECl (2 mol) are demineralized at 15 ° with 110 parts Water mixed and then started with the addition of 50 parts (1 mol) of tetramethylethylenediamine, the temperature between 35 and 40 ° is held. After cooling to 25 °, 79.8 parts (2 mol) of epichlorohydrin are added added (duration approx. 1 hour) and the temperature increases Held at 25 °. It is left at 40 ° overnight.

Examples 5-20

In each of the following examples, 1 mole of the coupling component is used of the examples mentioned reacted with 2 moles of a monofunctional amine, where compounds of the formula

-U-

Case 370-3710 F / C

Θ © θ

R ₀ NC - NO. χ 2 Cl

3 ρ

can be obtained. The reaction is continued until the Cl content remains constant. The reactants, conditions, etc. are given in Table 1 below. When adding additional solvent L. is its amount based on the amine (parts by weight: amine = 1)

Tabel

E.g.

Coupling comp. De example

Amine RN 3 additional
solvent

Reaction conditions

10

11

12 13

2 2

2 1

1 1 ethanol
(3.7 parts)

N (C ₂ H ₄ OH) ₃

NH "A.ethylene glycol methyl ether (0.8
Parts); Ethanol
(3.9 parts)

Coco fatty dialkylamine (R) NH (see below)

diethoxylated algae fatty amine

(see below)

'ettmonoalkylamin l _f NH ₂ (see below) ethylene glycol methyl ether
(0.33 parts)

Reflux for 5 hours, then distilling off the ethanol

Reflux 8 hours, pH 7 by adding 30% NaOH

85-95 ° / 4 hours 60-70 ° / 4 hours 65-75 ° / 3 hours

60 ° / 4 hours, then 80 ° / 1 hour, 90 ° / 2 1/2 hours, 90 ° / 3 hours.

85 ° / 20 hours

110 ° / 20 hours (product is waxy)

95 ° / 10 hours (product is a solid wax soluble in ethanol

60-70 ° / 3 1/2 hours

75 ° / 1 hour then 90 ° / 21 hours

Case 370-3710 F / C

E.g. Clutch
Comp. Des
Example Amine R "N Additional
solvent Reaction conditions 16 1 Fatty dialkylamine
(R _f ) ₂ NH (see below) like example 15 like example 15 17th 1 Dimethyl monococo-
fettamin RN (CH ")"
(\ ^{c 1} ' 70 ° / 1 hour then
90 ° / 2 hours 18th 3 2 4 * 85-95 ° / 4 hours 19th 4th (riTj \ 7J / O * 7 ζ * 7
\, L.li, J-IN ^ Ζ /, _) Λ 90 ° / 10 hours aqueous solution) 20th 4th see example 13 95 ° / 10 hours

The coco fatty alkyl group R has the following composition:

The tallow alkyl group R _t (hardened) has the following composition:

Caproyl (C6) 0.5 Parts Myristyle (C14) 3.5 Parts Caprylyl (C8) 8.0 Parts Pentadecyl (C15) 0.5 Parts Caprylic (ClO) 7.0 Parts Palmityl (C16) 30.0 Parts Lauryl (C12) 50.0 Parts Margaryl (C17) 1.5 Parts Myristyle (C14) 18.0 Parts Stearyl (C18) 62.5 Parts Palmityl (C16) 8.0 Parts Myristoleyl (C14) 0.5 Parts Stearyl (C18) 1.5 Parts Palmitoleyl (C16) 0.5 Parts Oleyl (C18) 6.0 Parts Oleyl (C18) 1.0 Parts Linoleyl (C18) 1.0 Parts

The fatty alkyl group R has the following composition:

C13 alkyl 70 parts

C15 alkyl 30 parts

wherein 50 parts straight-chain and 50 parts branched (mainly 2-methyl) are.

Example 21

The compound from Example 1 (aqueous preparation) (1 mol) is on 40-50 ° heated and then 174 parts (2 mol) of the following commercially available diamine mixture: 30-36% hexamethylenediamine and 64-70% diaminocyclohexane - added dropwise within 1 1/2 hours. Stirring is continued for 4 hours at 50 °, after which the analysis shows the theoretical one Menga to Cl. The product corresponds to the above formula XI ..

Case 370-3710 F / C

Examples 22-30

In each of these examples, 2 moles of the coupling component from Example 1 are reacted with 1 mole of the bifunctional amine indicated in Table 2, the compounds of the following type
develop:

Cl-C-B-C-Cl P P

The reaction conditions are also shown in Table 2 below evident

Tabel

E.g.

22 23

24 25

26th

27 28

29 30

Bifunctional amines

R NHCH-CH ₀ CK ₀ NH ₀ c λ 2. λ λ

(R = coco fatty alkyl) (see above) c

1,4-diazabicyclooctane

Additional
solvent

Industrial alcohols
Part)

Reaction conditions

60 ° / 2 hours

40 ° / 2 hours, then 60 ° / 1 hour 85 ° / 2 hours, then 95 ° / 1 hour

60 ° / 2 hours

60 ° / 1 hour, then 80 ° / 4 hours

60 ° / 1 hour, then 80 ° / 4 hours

85 ° / 4 hours

40 ° / 4 hours, then 60 ° / 2 hours

85-90 ° / 18 hours

50 ° / 1 hour, then 90 ° / 2 hours

Examples 31-4

In each of the following examples, 1 mole of a compound is the
Examples 22-30 reacted further with 2 moles of a monofunctional amine, resulting in compounds of the following type:

3: 11336

Case 370-3710 F / C

R-N-C - B - C - NR, ρ ρ

χ 2 Cl

The reaction components and the conditions are from the table below 3 can be seen.

Tabel

E.g.

31 32 33 34

35 36 37

38

39 '40 41

Pontic from example

22 23 22 25

25 25 26

26th

26 30 30

N (CH ₂ CH ₂ OE) ₃ N (CH ₂ CH ₂ OH) ₃ HN (CH ₂ CH ₂ OH) ₂

(CEg) ₂ KH (60% aq. Solution

like example

Amine

I ₂ NH (60% aq. Solution)

! oVnh "

N (CH ₂ CH ₂ OH) ₃ N (CK ₉ CH ₂ OH) ₃

(R _f ) N (CH ₃ ) ₂

(R = fatty alkyl, see above)

Additional solvent

Isopropanol (4.7 parts) + ethylene glycol (4.7 parts)

Reaction conditions

85-95 ° / 4 hours 95-98 ° / 3 hours 60-70 ° / 4 hours 40 ° / 3 hours, then 70 ° / 1 hour.

50 ° / 1 hour, 80 ° / 7 hours 60-70 ° / 3 1/2 hours

40 ° / 3 hours, then 70 ° / 1 hour

60 ° / 4 hours, then 80 ° /] hours 90 ° / 2 1/2 hours, 95 ° / 3 hours.

85-95 ° / 4 hours
95 ° / 16 hours
90-95 ° / 16 hours

example

Oil-polluted industrial wastewater, which contains approx. 4% oils and fats and which are contaminated with further industrial waste are treated with various flocculators. That used here Greasy wastewater contained a mixture of mineral oil and grease residues from the metal industry.

- 18 - Case 370-3710 F / C

Hichtionogenic surfactants (polyethylene glycols, ethoxylated higher alcohols or phenols) only had a limited effect when used in high quantities. Al Cl ₃ caused flocculation at 2000-5000 ppm, but with the inclusion of water, even then the aqueous phase was cloudy. Below 1000 ppm, Al Cl _{g was} ineffective, as was Ca Cl and Fe Cl. The product of Example 7 already causes flocculation at 200 ppm. and phase separation within 24 hours. The (upper) oil layer was homogeneous and the (lower) aqueous phase was clear and colorless.

Example 43

Here the pollution of the oily kind (f ^ 4%) was a mixture of animal fat and mineral oil as the main component and small amounts of fatty acid esters and fatty alcohols, fat additives, emulsifiers and industrial waste water also from the metal industry.

Inorganic flocculants hardly showed any effect. The product of Example 8 was fully effective at 10,000 ppm, that of Example 7 at 5000 ppm, and that of Example 31 at 1000 ppm Phase separation, which was completed within 2-3 days and resulted in a homogeneous oil layer and a transparent, slightly colored, aqueous one Shift led.

Example 44

Wastewater from the steel industry that contains 1.03% rolling oil in the aqueous Phase contained were treated with the agents according to the invention.

a) the products of Examples 13, 17 and 19 were effective between 1000 and 5000 ppm. A flocculated oil layer and an oil layer resulted slightly cloudy aqueous phase;

b) the products of Examples 40 and 41 gave at 1000-5000 ppm.

a rather cloudy aqueous phase and an almost anhydrous oil layer;

c) the products of Examples 16, 34, 37 and 38 were at 500-1000 ppm effective, the appearance was similar to. under a);

- 19 - Case 370-3710 F / C

d) the product of Example 15 was effective at 500-750 ppm. The watery Phase was much clearer here than under a). There were 14,000 l of the above waste water in a tank with 750 ppm of the product of the example 15 staggered. The tank contents were mixed well by pumping (6 minutes) and then left at 28 ° for 40 hours. The aqueous layer then contained only 0.046% oily components. The flocculated upper layer was heated to 60 ° after separation and contained after 1 hour only 1.3% water.

Example 45

A bitumen processing plant (oxidative treatment) delivered Distillate which consisted of λ / 60% water and λ / 40% oil (water-in-oil mixture). The products of Examples 5, 13, 14 and 19 were effective at 1000-2000 ppm. and provided a phase separation with a clear slightly brownish aqueous phase. The separation happened faster at 40-50 ° (the temp, the distillate) and could by increasing the temperature still to be improved.

29,000 l of the above-described water-in-oil emulsion with a water content of 62.4% (pH 9.6), 1000 ppm of the product from Example 13 were added at 50 °. The pH was adjusted to a value of 7 with HCl adjusted. Good mixing was achieved by pumping for 30 minutes. The phase separation began immediately and was complete after 15 hours.

An anhydrous oil layer and a clear aqueous phase resulted, the latter of which was suitable for being discharged into the public sewage system.

Claims (2)

SANDOZ PATENT GMBJJ 7850 Lörrach Case 370-3710 / F / C QUATERNAERE AMMONIUM COMPOUNDS AND THEIR USE AS FLOCKULATION AGENTS Patent claims 1. / Flocculant or emulsion-breaking agents, consisting of or containing compounds of the formula I. HaI-CH ₀ -CH-CH -Ng Z ₁ Z, ^ - OH ?1 CH-CH-CH-HaI 2 _t ί OH where Hai is chlorine or bromine, preferably chlorine, R and R, independently of one another, are C ₁ -C ₅ -alkyl or C ₂ -C ₅ -hydroxyalkyl groups, Y is a C -C _r -alkyl group, a 2-hydroxy-1,3-propylene- 2 6
group or one of the groups -CH -NH-CO-NH-C ₂ H ₄ - or -C H -NH-CO-NH-C H-, as well as their hydrolysis pro- 3 6 3 6 products and reaction products with ammonia and / or non-polymeric mono- and / or bifunctional amines, and χ is an integer from 0 to 7, where when χ is greater than 2, each of the symbols Y need not be the same. 2. Composition according to claim 1, consisting of or containing compounds of formula II C -BJ ₁ C -Χ [Α ^Θ ] P k ρ m II, wherein C is a group of the formula I of claim 1 without a shark, P. to * * mm O _ Case 370-3710 F / C is a group of formula III R ¹ R ¹ -JP- D-JP- R ' III, wherein the radicals R ^1, which may be the same or different, represents hydrogen, a C _ _2Q alkyl, C alkenyl, a Cg-hydroxyalkyl, an aralkyl or a group of formula IV IV, η --CH- CK- 0 - \ - H in which R can be H or methyl and η is a number from 2 to 150, preferably 2 to 50, · and the. Group R ₁ - glei.ch or can be different, D is a C "" alkylene group or one of the formula V V, 2> f where e is a number from 1 to 5, d and f independently of one another numbers from 2 to 5 and R, hydrogen, a C ₁ , alkyl, a C "-hydroxy-alkylo I ~ o / - o or a C haloalkyl group or a radical of the formula 1 6 (CH CH ₂ can be, 2'g 7 2
wherein g and h are independently numbers from 0 to 3 and R is a 5- to 7-membered ring system which can be wholly or partially unsaturated and which can be carbocyclic or a 0 and / or N-containing heterocycle, or B is a group of Formula VI
(R ¹ ) (R ¹ ) D ^{T (c} Vd - VI, - 3 - Case 370-3710 F / C in which D ¹ together with the two N atoms one or more ring systems of 5-. forms up to 7-ring members, which can be saturated or unsaturated or aromatic and contain further N atoms, R ¹ and d have the above meaning and ρ and q independently of one another can be 0 or 1, each X independently of one another can be chlorine, bromine, hydroxyl or a group of the formula VII R-N- VII, wherein the groups R, which may be the same or different, _n represents hydrogen, a C, _ori alkyl, a C ₁ "" alkenyl group, a C, -1-Key 2-20 2-O Hydroxyalkyl, a C cycloalkyl, a phenyl, an aralkyl, alkaryl or a group of the formula IV can be
or both groups R, together with the N atom to which they are bonded, form a saturated or unsaturated 5- to 7-membered ring which can contain one or more 0 or further N atoms and alkyl-substituting ones in positions may have, which must not be adjacent to quaternary N atoms, or three groups R together with the N atom to which they are bound,
form a polycyclic ring, which further
May contain 0 or N atoms, or form a heterocyclic aromatic ring system which has one or more contains additional N atoms,
R ^f ^ _N _D — N ^@ - VIII, ^R R '
in which R 'and D have the above meaning and k is a number, preferably from 0 to 5, especially 0 or 1
is and - 4 - Case 370-3710 F / C A means an anion, where m is a number equal to the number of cationic sites in the molecule. 3 · Compounds of the general formula Ha X'fC - B -t C - X ^f [A®] Ha, P k ρ m wherein C, B, k, A and m have the meaning given in claim 2, X ^{1 has} the meaning of X, with the following restrictions for the case of k = o a) X ¹ cannot be chlorine or bromine, - b) if each X in the entire molecule is a group of the formula VII mentioned in claim 1, then if two radicals R in each of the X groups are C -C alkyl radicals, at least one of the other two R groups in the entire molecule, and if one R group in each of the X groups is an O.-C-alkyl group, at least one of the four other R groups in the entire molecule different from hydrogen, and c) if each X is a group of the formula VIII of claim 1, at least one group R 'is different from hydrogen. 4 · Flocculation and De-Emulsification Procedures Using the means according to .Anspr claims 1 and / or 2 or the compounds according to claim 3.