CH655248A5 - FLOCKULATION OR EMULSION-BREAKING AGENTS AND QUATERNAIRE AMMONIUM COMPOUNDS CONTAINED therein. - Google Patents

Description

The present invention relates to compounds having a plurality of quaternary ammonium groups and their use as flocculating or emulsion breaking agents.

DE-OS 1 795 392 discloses the preparation of bifunctional compounds of the formula IX below

Hal-CH2-CH-CH2 OH

H

N + -M

I.

* 2

fl

J, «2

CH2-CH-CH2-Hal OH

.0

* m

IX,

in which shark represents chlorine or bromine (preferably chlorine) and the other radicals have the meaning given in formula IX of claim 3. According to DE-OS 1 795 392, the abovementioned compounds IX are used to prepare crosslinked polyamide amines by reaction with secondary amines.

It has now been found that compounds of the type of the aforementioned formula and their hydrolysis products and reaction products with non-polymeric mono- and / or bifunctional amines are valuable flocculants and emulsion-breaking agents for the separation of oil-in-water or water-in-oil emulsions are. While reaction products with primary or secondary lower alkyl amines are known, such reaction products with other amines are new.

The present patent accordingly relates to the flocculation and emulsion-breaking agents mentioned in claims 1 and 3 and the new compounds specified in claim 2, which can be used for the stated purpose. Finally, the subject of the present patent is a flocculation and emulsion breaking process using the agents according to claim 1 or 3.

Preferred compounds of claim 2 are those of the formula Ia in which the group X 'is one of the formula VII mentioned in claim 1, especially those in which none of the groups R is hydrogen or those in which at least one R is one Is C8_I8 alkyl group. Also preferred are those compounds in which both X 'are the same.

If in the new connections k> 0, i.e. if two or more Cp groups are present in the molecule, these can of course be the same or different, they are preferably the same. The same applies to k> 1,

if 2 or more B groups are present in the molecule, 35 are preferably the same here as well.

According to DE-PS 1 795 392, compounds of formula IX are prepared by reacting an excess of epi-halohydrin (especially epi-chlorohydrin) with a monofunctional secondary amine (especially dimethyl-40 amine) or a bifunctional tertiary amine (for example tetra-methylethylenediamine (or mixtures thereof), this reaction taking place in an acidic medium, ie the amine is at least partially in salt form Preferred compounds of the formula IX are those in which R 1 and 45 R 2 are methyl, x = 0 or 1, preferably 1 and Y is the 2-hydroxy-1,3-propylene group.

These compounds of the formula IX are referred to below as “coupling components”. Your two reactive halogen atoms can be drolized as is known, or react with monofunctional primary or secondary lower alkylamines, resulting in terminal amines (or their salts). The agents according to the invention can contain or consist of these known compounds, i.e. the active substance 55 can be one of the formula IIb.

X "-Cp-X" [Ae],

IIb,

wherein Cp, A 9 and m have the meaning given in the claims and each X "(independently of one another) is a chlorine, bromine or the group

K - ©

65

can be in which R3 is hydrogen or CM-alkyl and R4 is CM-alkyl.

655 248

4th

Under alkaline conditions, the amine salts can be converted to the free form and Formula IIb is intended to encompass both the salts and the free amines.

©

©

© -,

H N-D-NH f C -NH -D-NH, 2 2 p 2 2 1

wherein Cp, D, k, A® and m have the meaning given in the claims. The compounds of type Ile are also suitable agents according to the invention.

The “coupling component” can also be reacted with ammonia, mono- or bi-functional amines, preference being given to monofunctional tertiary amines of the formula R3N (that is to say those in which R is not hydrogen). The R groups are preferably C1_20-alkyl or C2_6-hydroxyalkyl radicals. Primary, secondary or tertiary amines with at least one Q ^ g alkyl group are further preferred.

Preferred tertiary amines are those in which all three radicals R C2_4-hydroxylalkyl, especially the hydroxyethyl radicals or one of the groups R Cg_lg-alkyl, especially CI0_i4-alkyl, and the two other C ^ alkyl, especially methyl or C ^ - Hydroxylalkyl, especially hydroxyethyl, are.

Preferred primary or secondary amines for the reaction with the “coupling component” are those in which the R groups which are not hydrogen are preferably C 1 -C 4 -alkyl, C 2 -C 4 -hydroxyalkyl or benzyl radicals. Particularly preferred primary and secondary amines are long-chain alkylamines with at least one C8_lg alkyl group, such as cocoamine or tallow fatty amines.

When reacting with monofunctional tertiary amines, quaternary ammonium compounds are formed (at every point in the molecule where the reaction takes place), the further reactivity of which ceases. Monofunctional tertiary amines are therefore to be regarded as end groups or they serve to complete the reaction sequence. Even when reacting with ammonia or monofunctional primary or secondary amines, the further reaction is ruled out by the salt formation that has occurred, unless there is neutralization with bromine. In contrast, in the case of bifunctional amines, the ratio of the reactants to one another can be used to check whether there are free amino groups or halogen groups at the ends of the molecules, which can then react further in each case. A bifunctional amine can therefore be seen as a bridge for a possible molecular enlargement.

For the purposes of the present invention, an amine is to be regarded as “bifunctional” if it contains two reactive amino groups which react easily with the “coupling component”; Such amines are also "bifunctional" which additionally contain less reactive amino groups, i.e. those that are more difficult to react. Such a "bifunctional" amine is e.g. B. the diethylenetriamine (H2N-C2H4-NH-C2H4-NH2).

Preferred groups B are those of the groups of the formula III given above, in which R 'independently of one another is hydrogen or methyl and D is a C2_I2-alkylene radical, preferably -C2 H4-, - (CH2) 6- or - (CH2), 2 - or is a group of the formula V in which e = 1, d and f are independently 2 or 3 and R6 is hydrogen. B can also be a group of the formula VI in which D 'forms a piperazine ring with the nitrogen, each p = 1, R' = H and q = 0.

It is also known that the above-mentioned “coupling component” leads to compounds of the formula Ile in the reaction with an excess of a di-primary amine (for example di-ethylenetriamine).

©

-nh2-d-nh2

C Ae]

in

Ile,

Further preferred classes of groups B are those of formula III in which three R 'are hydrogen and one group R' is a C8-20 alkyl, especially a Cu5 alkyl group.

For example, two moles of the “coupling component” Cl-Cp-Cl can first be reacted with a mole of a diamine (R ') 2N-D-N (R') 2 to give a compound of the formula.

x 2 cl

©

25th

R 'R'

<+) '©'

Cl-C -N-D-N - C-Cl

P. . P

, R 'R'

and further end-capped with 2 moles of a monofunctional amine (R) 3N to a compound of the formula

R »Rl

R \ @ © '©' © ^ R ©

R - N - C - D - N - C - S- R x 4 Cl

R

P t R '

I.

R *

If the ratio of the bifunctional amine to the “coupling component” is increased in the first step, 30 as can be seen, the number of units can be increased, a linear polymer compound being formed with equimolar amounts. With a further increase in the amine component, compounds with terminal amino groups are formed and with a ratio of bifunctional amine to the “coupling component” of 2: 1, compounds of the formula are formed

40 R "

R '

R '

© a-

l o

- ri

. p

1

R '

R *

, R '

VR '

x 2 cl

©

©

Such compounds can now be reacted with another “coupling component” Cl-Cp'-Cl and then end-capped with a tertiary amine to give compound 45 of the formula

R 'R * R' R '

■ ^ v. © <ff) <(£) »fT \ t (t \ R

R-N-C'-N -D-> P-C -NJ-D-N -C'-N- R x 6 Cl T> P I. P. , P \ p 50 R 'R' R 'R "

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

It can be seen that if one or both of the R 'are hydrogen, the cationic group -N® (R') 2 is an amine salt and not a quaternary ammonium salt. During neutralization, secondary amines (-NH-) or tertiary amines (-NR-) are obtained with deprotonation. The basicity and water solubility of such a compound is of course different from that of the salt. The same considerations apply to the end groups (R) 3N®- if one or more R are hydrogen.

The special properties of the compounds or agents according to the invention depend on the chain length 65 of the molecules, their spacing between the quaternary groups in the chains and the nature of the side chains or subgroups. For the normally water soluble compounds e.g. by incorporating many lipophilic be

655 248

chains can be changed until water insolubility.

The anion A® will usually be that of the acid that was used for the production of the “coupling component” and that halogenamion from the epihalohydrin used. When using HCl and epichlorohydrin, all Ae are chlorine anion Cl®. Of course, the anions in the end products can be exchanged in a known manner.

Of course, with a polyvalent anion e.g. S04ee the symbol A® for Vi S04®®.

Mixtures of the compounds of the formula I can be obtained by using mixtures of starting materials or intermediates (in the case of a gradual build-up).

The «coupling component» itself or such end products with terminal halogen residues (e.g. the formula on page 4) can be hydrolyzed (with aqueous alkali) and thereby provide 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 gradual structure, on those of the intermediates. In the case of reactive amines, the reaction is usually exothermic, even if the “coupling component” is in an aqueous solution. In this case, the reaction can be controlled by slowly adding a reaction partner, and the reaction may have to be kept under control by additional cooling. The initial temperatures are usually between 0 and 100 ° C, preferably 20-60 ° C. The upper temperature limit depends largely on the boiling point of the amine used and on the desired end product. In certain cases, one or the other reaction component or both may be in aqueous solution or may be reacted in the presence of water, which may also be present from the preparation thereof. In other cases, the absence of water will be advantageous or necessary and, if necessary, 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 pH during the reaction. A polar solvent is usually advantageous or necessary for homogeneous distribution in the reaction medium. Usually, it may be beneficial 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. Of course, the factors mentioned above will also influence the choice of the most suitable solvent; 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 consequently also influenced by this. The reaction temperatures in such cases are usually above 60 ° C (up to 100 ° C). Are suitable for. B. lower alcohols, e.g. B ethanol and n- and iso-propanol and glycols such as ethylene glycol or their ether. If desired, the solvent can be distilled off or, in the case of a gradual build-up, remain in the reaction medium or, under certain circumstances, even form a component of the end product.

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

The control of the reaction course can, for. B. by s measurement of the consumption of the amine (or the "coupling component") or with gradual build-up of the intermediate component or by measuring the ion formation, z. B. from the a-chloro-ß-hydroxyethyl group of the "coupling component" by determining the chlorine-lo ions. The reaction is complete when the theoretical amount of Cl® ions has formed or when their concentration remains constant after a certain time.

Hydrolysis of the halogen end group (to hydroxyl) can e.g. B. in dilute aqueous sodium hydroxide solution at temperatures up to 60 ° C.

The compounds of the formulas I, IX and IA have surface-active activity, on the basis of which they can be used as flocculants or also as emulsion-breaking agents. Oil-in-water and water-in-oil 20 emulsions can be separated effectively by means of the preparations according to the invention. Flocculation in the sense of the present invention means the initial stage of de-emulsionation. In oil-in-water emulsions, flakes form individual oil droplets, which further coagulate to larger aggregates. If the breaking of the emulsions does not go beyond this stage, i.e. If the “flakes” do not separate completely, they usually still contain so much water that they cannot be used for incineration or further processing without additional treatment.

The agents according to the invention predominantly bring about in a second phase the complete unification of the “flakes” into an oil layer which hardly contains any water. This process, namely the transition from «Flok-35 ke» to a separate oil phase, can be accelerated by heating.

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

40

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: 45 35-40 °). With cooling and constant stirring, 2093 parts (3 mol) of epichlorohydrin are then added, the temperature being kept at 35-40 °.

When the addition is complete, the mixture is left to react for 8 hours at 35-40: and cooled 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 mol) are slowly added to 150 parts of a 60% dimethylamine solution (2 mol) 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 exceed 40 °. The mixture is stirred at 50 ° for 1 hour and left to stand overnight.

Example 3

121.67 parts of 30% HCl (1 mol) is slowly added to 210 parts of diethanolamine (2 mol) (temperature <40 °). 65 After the addition has ended, 277.5 parts (3 mol) of epichlorohydrin are added at 35 ° in such a way that the reaction temperature does not rise above 40 °. The mixture is stirred at 50 ° for 1 hour and left to stand overnight.

655 248

6

Example 4

86.3 parts of 36.5% HCl (2 moles) are mixed at 15 with 110 parts of demineralized water and then the addition of 50 parts (1 mole) of tetramethylethylenediamine is started, the temperature being kept between 35 and 40. After cooling to 25 ", 79.8 parts (2 mol) of epichlorohydrin are added (duration approx. 1 hour) and the temperature is kept at 253. The mixture is left at 40 ° overnight.

Examples 5-20 In each of the following examples, 1 mol of the coupling component of the examples mentioned is reacted with 2 mol of a monofunctional amine, compounds of the formula

©

©

R_N - C - NR 3 p 3

x 2 cl

©

be preserved. The reaction is continued until the Cl® content remains constant. The reactants, conditions, etc. are given in Table I below. If additional solvent is added, its amount is based on the amine (parts by weight: amine = 1).

Table 1

E.g. clutch comp. of the example

Amine R, N

Additional solvent reaction conditions

9

10th

11

12

13

14

15

16

17th

18th

19th

20th

1

2 2

1

1

2 1

1 1 1 1

3rd

4th

(C2Hs) 3N

<o) -se2

N (C2H4OH) 3 HN (C, H4OH) 2

0NH2

<§> -ch2nh2

(n-C4H9) 3N

Ethanol (3.7 parts)

Coco fatty dialkylamine (Rc) 2NH (see below) diethoxylated tallow fat amine RtN (C2H4OH) 2 (see below)

Ethylene glycol monoethyl ether (0.8 parts); Ethanol (3.9 parts)

N

Fatty monoalkylamine RfNH2 (see below)

Fatty dialkylamine (Rf) 2NH (see below) Dimethylmonococofettamin-RcN (CH3) 2 (see below) N (C2H4OH) 3

(CH3) 3N (27.5% aqueous solution)

see example 13 -

The coco fatty alkyl group Rc has the following composition:

Reflux for 5 hours then distilling off the ethanol

Return 8 hours, pH7 by adding 30% NaOH

85-9574 h

60-7074 h

65-7573 h

6074 hrs, then 80 ° / l hrs .; 90/2 ^ hrs., 9073 hrs.

85/20 h

110720 h (product is waxy)

95710 hours (product is a solid wax soluble in ethanol)

60-7073 / 2 hours

7571 hours then 9072I hours

as in example 15

7071 hours then 9072 hours

85-9574 h

90710 h

957IO h

The tallow fatty alkyl group Rt (hardened) has the following composition:

Ethylene glycol monoethyl ether (0.33 parts) as Example 15

Caproyl

(C6)

0.5 parts

Myristyl

(C14)

3.5 parts

Caprylyl

(C8)

8.0 parts

Pentadecyl

(C15)

0.5 parts

Capryl

(C10)

7.0 parts

Palmityl

(C16)

30.0 parts

Lauryl

(C12)

50.0 parts

Margaryl

(C17)

1.5 parts

Myristyl

(C14)

18.0 parts

Stearyl

(C18)

62.5 parts

Palmityl

(C16)

0.8 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 Rf has the following composition:

Cl 3 alkyl 70 parts, Cl 5 alkyl 30 parts wherein 50 parts are straight chain and 50 parts are branched (mainly 2-methyl).

7

655 248

Example 21

The compound from Example 1 (aqueous preparation) (1 mol) is heated to 40-50 and then 174 parts (2 mol) of the following commercially available diamine mixture: 30-36% hexamethylene diamine and 64-70% diaminocyclo-hexane - dropwise within 1 ' / Added 2 hours. The mixture is stirred at 50 ° for 4 hours, after which the analysis shows the theoretical amount of Cl®. The product corresponds to the formula on page 4.

Examples 22-30 In each of these examples, 2 moles of the coupling component of Example 1 are reacted with 1 mole of the bifunctional amine indicated in Table 2, giving the compounds of the following type:

Cl-Cp-B-Cp-Cl

The reaction conditions are also shown in Table 2 below

10th

Table 2

For example, bifunctional amines

Additional solvents

Reaction conditions

22 H2NCH2CH2NH2

23 HN 'NH

6072 h

4072 hrs, then 60/1 hrs 8572 hrs, then 95/1 hrs

24 H2NCH2CH2CH2NH2

25 H2N (CH2) 6NH2

26 H2N (CH2) 12NH2

27 HnQî-CH2CH2NH2

28

29

30th

H2NCH, CH2NHCH2CH, NH2 -

6072 hours 60/1 hours, then 80'74 hours 60/1 hours, then 8074 hours

8574 h

40J / 4 hours, then 6072 hours

RcNHCH2CH2CH2NH2 industrial alcohols (1 part) 85-90718 h

(Rc = coco fatty alkyl) (see above)

1,4-diazabicyclooctane -

5071 hrs, then 9072 hrs

Examples 31-41 In each of the following examples, 1 mol of a compound from Examples 22-30 is further reacted with 2 mol of a monofunctional amine, compounds of the following type being formed:

© ©

R, N - C - B - C - NR 3 P P 3

x 2 cl

©

The reaction components and the conditions are shown in Table 3 below.

Table 3

Example bridge link from example

Additional solvent reaction conditions

31

32

33

34

39

40

41

22

23 22 25

35 25

36 25

37 26

38 26

26 30 30

N (CH2CH2OH) 3 N (CH2CH2OH) 3 HN (CH2CH2OH) 2 (CH3) 2NH (60% aqueous solution) as Ex. 13

3rd

(CH3) 2NH (60% aqueous solution)

®-NH_

N (CH2CH2OH) 3 N (CH2CH2OH) 3 (Rr) N (CH3) 2 (Rf = fatty alkyl, see above)

85-9574 h

95-9873 h

60-70o / 4 hours

4073 hrs, then 7071 hrs

5071 h, 8077 h

60-7073 '/ 2 hours

4073 hrs, then 7071 hrs

6074 hrs, then 8071 hrs. 9072/2 hrs., 9573 hrs.

85-9574 hrs. 95716 hrs. Isopropanol (4.7 parts) + 90-95 / 16 hrs. Ethylene glycol (4.7 parts)

655 248

8th

Example 42

Industrial waste water contaminated with oil, which contains approx. 4% of oils and fats and which is contaminated with further industrial waste, is treated with various flocculants. The grease-contaminated wastewater used here contained a mixture of mineral oil and fat residues from the metal industry.

Non-ionic surfactants (polyethylene glycols, ethoxylated higher alcohols or phenols) had only a limited effect when used in large quantities. AI Cl3 caused flocculation at 2000-5000 ppm, but including water, even then the aqueous phase was cloudy. Al Cl 3 was ineffective below 1000 ppm, likewise Ca Cl2 and Fe Cl3.

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 oily type of contamination (~ 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 showed little 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 and causes gradual phase separation, which was completed within 2-3 days and resulted in a homogeneous oil layer and a transparent, slightly colored, watery layer.

Example 44

Wastewater from the steel industry, which contained 1.03% rolling oil in the aqueous phase, was treated with the agents according to the invention.

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

b) the products of Examples 40 and 41 provided a rather cloudy aqueous phase and an almost anhydrous oil layer at 1000-5000 ppm;

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

io d) the product of Example 15 was effective at 500-750 ppm. The aqueous phase was much clearer here than under a). 14 0001 of the above Waste water in a tank with 750 ppm of the product of Example 15. 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 607 after separation and contained only 1.3% water after 1 hour.

20 Example 45

A bitumen processing plant (oxidative processing) supplied a distillate consisting of ~ 60% water and ~ 40% oil (water-in-oil mixture). The products of Examples 5, 13, 14 and 19 were effective at 251000-2000 ppm and provided phase separation with a clear, slightly brownish aqueous phase. The separation happened faster at 40-50 ° (the temp. Of the distillate) and could be improved by increasing the temperature.

29,0001 of the above-described water-in-oil emulsion 30 with a water content of 62.4% (pH 9.6) was mixed at 50 ° with 1000 ppm of the product from Example 13. The pH was adjusted to 7 using HCl. A good mixture was achieved by pumping for 30 minutes. The phase separation started immediately 35 and was completed 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 wastewater.

50

55

60

s

Claims (4)

655 248 2nd PATENT CLAIMS 1. Flocculation or. emulsion breaking agents consisting of or containing compounds of formula I. X -t Cp - B -J- | ç Cp - X / Pf 'P "" P wherein Cp is a group of formula II m I, -ch2-ch-ch2 - OH N.H-Y r2 N +. R2 ch2-ch-ch2- OH' alkyl or a C ^ haloalkyl group or a radical of the formula - {CH2 * g R7 - (CH2tR-ist, s where g and h are independently numbers from 0 to 3 and R7 is a 5- to 7-membered ring system which can be wholly or partly unsaturated and which is carbo-io cyclic or a heterocycle containing oxygen and / or nitrogen, or B is a group of formula VI II, 15 wherein Rj and R2 are independently Ci-C5-alkyl or C2-Cs-hydroxyalkyl groups, Y is a C2-C6-alkylene group, a 2-hydroxy-1,3-propylene group or one of the groups -C2H4-NH-CO-NH-C2H4- or -C3H6-NH-CO-CH-C3H6-, x is an integer from 0 to 7, and if x is greater than 2, each of the symbols Y need not be the same, A 9 represents an anion and m is a number equal to the number of cationic sites in the molecule, B is a group of formula III \ D * <R '> / P N, © R '' % ' R ' VI, R ' -N + i R * R ' I. - D - N + -I R ' 20 in which D 'together with the two N atoms forms one or more ring systems from 5- to 7-ring members, which is saturated or unsaturated or aromatic and can contain further N atoms, 25 R 'and d have the above meaning and p and q are independently 0 or 1, each X independently of one another chlorine, bromine, hydroxyl, a group of formula VII HI, Rv © "7" - VII, wherein the radicals R ', which may be the same or different, represent hydrogen, a C 1-20 alkyl, a C2-220 "alkenyl, a C2-6 hydroxyalkyl, an aralkyl or a group of the formula IV f CH - CH- 0 - • H l * 5 IV, n in which Rs is H or methyl and n is a number from 2 to 150, and the groups R5 can be the same or different, D is a C2-20 alkylene group or one of the formula Vist ^ 4CH2) d - NR6-J-5 tCH2) f- v> 35 wherein the groups R, which may be the same or different, represent hydrogen, a C, _20-alkyl, C2_20-alkenyl, C2_6-hydroxyalkyl, C3_8-cycloalkyl, phenyl, aralkyl, alkaryl group or one Group of the formula IV or 40 groups R, together with the N atom to which they are attached, form a saturated or unsaturated 5- to 7-membered ring which may contain one or more O or other N atoms and may have alkyl substituents in positions which must not be adjacent to quaternary 45 N-atoms, or three groups R together with the N-atom to which they are attached form a polycyclic ring which further O- or N- May contain atoms, or is a group of formula VIII R ' R R ' N® I R ' VIII, where e is a number from 1 to 5, d and f are independently numbers from 2 to 5 and R6 is hydrogen, a CM alkyl, a C2_6 hydroxy 55 in which R 'and D have the above meaning and k is a number from 0 to 5. 2. Composition according to claim 1, consisting of or containing compounds of formula IX Hal-CH2-CH-CH2 CM ?1 «2 N ++ Y l fi N + I. * 2 CH2-CH-CH2-Hal OH A Q m IX, 3rd 655 248 wherein Shark is chlorine or bromine, R 1 and R 2 are independently C 1 -C 4 -alkyl or C 2 -C 5 -hydroxyalkyl groups, Y is a C2-C6-alkylene group, a 2-hydroxyl-1,3-propylene group or one of the groups -C2H4-NH-CO-NH-C2H4- or -C3Hfi-NH-CO-NH-C3H6-, x is an integer from 0 to 7, and if x is greater than 2, each of the symbols Y need not be the same, A 9 represents an anion and m is a number equal to the number of cationic sites in the molecule. 3. Compounds of the general formula Ia B c - Jk p X 'A 0 R in each of the X 'groups are C, -C4-alkyl radicals, then at least one of the other two R groups in the total molecule is different from hydrogen, and if a radical R in each of the X' groups is a C, -C4- Is alkyl, then 5 at least one of the four other R groups in the total molecule is different from hydrogen, and c) if each X 'is a group of the formula VIII mentioned in claim 1, at least one group R' is different from hydrogen. 4. Flocculation and emulsion breaking processes using the agents according to claim 1 or 2. m where Cp, B, k, A9 and m have the meaning given in claim 1, X 'has the meaning of X, with the following restrictions for the case of k = 0 a) X 'cannot be chlorine or bromine, b) when each X 'in the total molecule is a group of the formula VII mentioned in claim 1 and when two radicals