IT8148180A1 - QUATERNARY AMMONIUM COMPOUNDS USABLE AS FLOCCULATION AGENTS OR EMULSION BREAKING AGENTS - Google Patents

Description

DESCRIPTION of the industrial invention entitled:

"Quaternary ammonium compounds usable as flocculation agents or emulsion breakers."

SUMMARY OF THE INVENTION

The invention relates to the application of quaternary ammonium compounds of formula I

R,

I

Do you have? CH-? CH? CH5 N Y CH ~? CH? CH-Ha1 (I)

2 ! ?

OH R2 A.?' 2 OIH 2

X

where Hai means a chlorine or bromine atom, R^ and R^ each represent an alkyl or hydroxyalkyl group, Y means an alkylene group, 2-hydroxy-1,3-propylene, -CH^CH^NHCONHCH^CH^- or -CH^CH^CH^NHCONHCH^CH^CH^-, A^ represents an anion, and x means an integer between 0 and 7,

as flocculation agents or demulsifiers for emulsions.

The present invention relates to compounds containing multiple cationic groups.

British Patent No. 1213745 describes the preparation of the bifunctional compounds of formula 1.

R, R,

(i) Have you? CH_? CH? CH; N or CH~? CH? CH0Hal '0 2 ! 2

OH R2 A?'> R2 0 OH

in which

Hai means an atom of chlorine or bromine, preferably chlorine,

R^ and R2 each represent, independently of each other, an alkyl group containing 1 to 5 carbon atoms or a hydroxyalkyl group containing 2 to 5 carbon atoms,

Y means an alkylene group containing 2 to 6 carbon atoms, a 2-hydroxy-1,3-propylene group, -CH2CH2HHCONHCH2CH2- or -CH CH C^NHCONHCHjCH CH -,

,?

A represents an anion, and

x means an integer between 0 and 7, the symbols Y not necessarily having the same meaning when x means a number greater than 2.

According to the above-mentioned patent, the compounds of formula I are used for the cross-linking of polyamides by reaction with secondary amino groups in the polymer chain.

The applicant has now found that the compounds of formula I, together with their hydrolysis products and their reaction products with compounds selected from ammonia and nonpolymeric monofunctional animines and nonpolymeric bifunctional animines, are suitable as demulsifiers for flocculation or breaking oil-in-water emulsions. Although the compounds of formula I and their reaction products with primary and lower secondary alkylamines are known, their reaction products with other animines are new.

The present invention therefore relates to a process for the flocculation or breaking of an emulsion, characterised in that the emulsion is treated with a compound of formula II.

(II)

X C ? B

P CP m

where 0^ represents the remainder of a compound of formula I from which the halogen atoms have been eliminated, i.e. corresponding to the formula

lx

-CH--CH-CH= ? -CH. CH-CH-s?

2 ?H 2 I 2

OH

X

where R, R2, Y and x have the meanings already indicated;

B represents a group of formula III

R' R?

r N (III)

I?

R* R'

wherein the R* groups, which may be identical or different, are selected from hydrogen, alkyl groups containing from 1 to 20 carbon atoms, alkenyl groups containing from 2 to 20 carbon atoms, hydroxyalkyl groups containing from 2 to 6 carbon atoms, aralkyl and the groups of formula IV

CH ? CH ? 0 H

I (IV) *5 n

where n means a number between 2 and 150, preferably between 2 and 50, and the symbols R,. each represent, independently of each other, a hydrogen atom or a methyl group, and

D represents an alkylene group containing 2 to 20 carbon atoms, a group of formula V

(V)

-NR

fCH2Jd ?*CH2>T

in which

and it means a number between 1 and 5,

d and f each represent, independently of each other, a number between 2 and 5, and

R^ means a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, hydroxyalkyl containing 2 to 6 carbon atoms, or haloalkyl containing 1 to 6 carbon atoms,

or a group of formula-(CH ?}? R-?(CH where g and h mean ^ 8 ? ^ n

each, independently of each other, is a number between 0 and 3 and R^ represents a cyclic system with 5-7 chains that can be saturated or completely or partially unsaturated and that can contain only carbon atoms or a mixture of carbon, oxygen and/or nitrogen atoms, or

B represents a group of formula VI

R' ). R' (vi) \ I

<CH2>d N

* j q

where D1, together with the two nitrogen atoms, represents a cyclic system containing one or more 5-7 chain rings which may be saturated, unsaturated or aromatic and which may contain other nitrogen atoms,

R' and d have the meanings already indicated, the symbols p and q each mean, independently of each other, 0 or 1;

the symbols X each represent, independently of each other, a chlorine or bromine atom, a hydroxy group or a group of formula VII

R- N? (VII)

wherein the R groups, which may be identical or different, are selected from hydrogen, alkyl groups containing from 1 to 20 carbon atoms, alkenyl groups containing from 2 to 20 carbon atoms, hydroxyalkyl groups containing from 2 to 6 carbon atoms, cycloalkyl groups containing from 3 to 8 carbon atoms, phenyl, aralkyl, alkaryl and the above-mentioned groups of formula IV, or 2 R groups, together with the nitrogen atom to which they are bonded, form a saturated or unsaturated 5-7 chain ring which may contain one or more oxygen atoms or one or more additional nitrogen atoms and which may be substituted by an alkyl group at positions not adjacent to the quaternary nitrogen atom, or 3 R groups, together with the nitrogen atom to which they are bonded, form a polycyclic system which may contain one or more oxygen atoms or one or more additional nitrogen atoms and which may be substituted by an alkyl group at positions not adjacent to the quaternary nitrogen atom, contain additional oxygen or nitrogen atoms, or represent an aromatic ring system that may contain one or more additional nitrogen atoms,

or a formula group VIII

R'

R' (Viii)

\

N- N?-5?^-

/ R'

where R' and D have the meanings already indicated,

k means an integer, preferably between 0 and 10, especially between 0 and 5, more especially 0 or 1,

.0

A represents an anion, and

? means an integer equal to the number of cationic sites in the molecule.

The invention also relates to the new compounds of formula Ila

X' B C - X' A? (Ha)

P

k m

.0

where C, B, k. A and m have the meanings already indicated and the sym-P

balls X' have the meanings indicated for X, under the conditions that, when k = 0,

1) X1 is different from a chlorine or bromine atom,

2) when each symbol X' signifies a group of formula VII and when two R groups attached to each of the X' groups represent an alkyl group containing from 1 to 4 carbon atoms, then at least one of the two other R groups present in the molecule is other than hydrogen, and when one R group attached to each of the X' groups signifies an alkyl group containing from 1 to 4 carbon atoms, then at least one of the four other R groups present in the molecule is other than hydrogen, and

3) when each symbol X' represents a group of formula VIII, then in each group X' at least one group R' is different from hydrogen.

X' preferably represents a group of formula VII, in particular one in which all the R groups are other than hydrogen, or i.e. in which at least one R group signifies an alkyl group containing from 8 to 18 carbon atoms. Preferably, both X' groups are identical.

When k>0, i.e. 2 or more C groups are present

P

In the molecule, these can be identical or different, but are preferably identical. Likewise, when k>1, that is, two or more B groups are present in the molecule, these can also be identical or different, but are preferably identical.

According to British Patent No. 1,213,745, compounds of formula I wherein X denotes a chlorine or bromine atom are prepared by reacting a specific excess of epihalohydrin, preferably epichlorohydrin, with a functional secondary amine, e.g., dimethylamine, or with a bifunctional tertiary amine, e.g., tetramethylethylenediamine, or with mixtures thereof, in the presence of an acid that partially converts the amine to the amine salt. Preferred compounds of formula I are those wherein the symbols R^ and R^ each independently represent a methyl group, x denotes 0 or 1, preferably 1, and Y represents a 2-hydroxy-1,3-propylene group.

The compounds of formula I (hereinafter referred to as "coupling agents") have two terminal reactive halogen atoms; it is known that these compounds can be reacted with monofunctional primary or lower secondary alkylamines to obtain products having terminal amino groups in the form of salts. The process of the invention can be carried out using these known compounds, i.e., by flaking or demulsifying with a compound of formula IIb.

X"- C? X" (Hb)

P A? m

where C, A? and m have the meanings already indicated and the symbols X" P? which can be identical or different, each mean a chlorine or bromine atom or a group of formula

H

R?\ \?N

R'

where R^ represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms and R^ means an alkyl group containing 1 to 4 carbon atoms.

Under basic conditions, terminal amino groups in the form of salts can lose a proton to give terminal groups of formula R^R^N-, and the formula IIb is understood to encompass the reaction products, both in the form of amine salts and in the form of the free base.

It is also known that the coupling agent can be reacted with an excess of a di-primary amine such as diethylenetriamine to yield compounds of formula IIe.

? ? ? ?

H2N-D-NH 2 Cp-NH2-D-NH2 Cp-NH2-D-NH2 A ? (H e)

m

where Cp, D, k, A, and m have the meanings already indicated. The process of the invention can also be carried out using compounds of formula Ile.

The coupling agent can also be reacted with ammonia, monofunctional or bifunctional amines.

A preferred class of monofunctional amines are the monofunctional tertiary amines of formula (R)^N i where all the

R groups are different from hydrogen and mean preferably

an alkyl group containing 1 to 20 carbon atoms or a hydroxyalkyl group containing 2 to 6 carbon atoms. Another

The preferred class is primary, secondary, or tertiary amines that possess at least one alkyl group containing 8 to 18 carbon atoms.

Preferred tertiary amines are those in which all three R groups represent a hydroxyalkyl group containing 2 to 4 carbon atoms (preferably hydroxyethyl) or in which one R group means an alkyl group containing 8 to 18 (preferably 10 to 14) carbon atoms and the two remaining R groups each represent an alkyl group containing 1 to 4 carbon atoms (preferably methyl) or a hydroxyalkyl group containing 2 to 4 carbon atoms (preferably hydroxyethyl).

Preferred primary and secondary amines are those in which the R groups, other than hydrogen, represent an alkyl group containing 1 to 20 carbon atoms, a hydroxyalkyl group containing 2 to 6 carbon atoms, or a benzyl group. Particularly preferred primary and secondary amines are those containing at least one alkyl group containing 8 to 18 carbon atoms, such as coconut amines or hardened tallow fatty acid amines.

Reactions with monofunctional tertiary amines result in the formation of a quaternary ammonium group for each reacted amine molecule, and these terminal quaternary groups are incapable of further reaction. Monofunctional tertiary amines can therefore be considered as terminal groups that terminate the reaction sequence. Similarly, ammonia or monofunctional primary or secondary amines lead to the formation of cationic amino groups that are incapable of further reaction until neutralized with a base. On the other hand, reactions with bifunctional amines can be controlled by varying the molar ratio of the reactants so that free reactive halogen atoms or free amino groups remain at the ends of the molecule, and these groups are capable of further reaction. A bifunctional amine can therefore be considered as a bridge capable of

to extend the size of the molecule. An amine is called "bifunctional" when it has two reactive amino groups that react readily with the coupling agent, even if it also includes one or more less reactive nitrogen atoms that do not react so readily. Thus, for example, diethylenetriamine (H^N-C0H-NH-C_H-NH-) can be considered a bifunctional amine.

naie.

The preferred B groups correspond to formula III where the symbols R' each represent, independently of each other, a hydrogen atom or a methyl group and D means D", i.e. an alkylene group containing from 2 to 12 carbon atoms, preferably ^CH2^6 ? "^ 2^12* ? A SruPP? of formula V where e means 1, d and f each represent, independently of each other, 2 or 3 and R, means a 6 atom

d?hydrogen; or B represents a group of formula VI in which D' forms, together with the nitrogen atoms, a piperazinyl residue, the symbols p each mean 1, the symbols R' each represent a hydrogen atom, d means 2 and q represents 0 or 1.

Another preferred class of B groups are those of formula III where three R' groups mean a hydrogen atom and one R' group represents an alkyl group containing from 8 to 20, preferably from 11 to 15 carbon atoms, and D means D" as specified above.

Thus, for example, one can react two moles of a coupling agent Cl-C^-Cl, first with one mole of a diamine (R') N-D-NCR*^ to prepare a coupling agent of formula IX.

R' R'

? i (IX) Cl- c? D? ? c

I ? r Cl

R' R' 2C1'?

where the symbols C^, D and R' have the meanings already given, and then this compound can be reacted with 2 moles of a monofunctional amine (R)N to stop the reaction, which gives a compound of formula X

RR\ ? R?V?-* R

? N-C? N? D N'?? Ctj- ?N/? R (X)

R R'

4C1?

where the symbols C^, D, R and R' have the meanings already indicated.

By increasing the ratio of the difunctional amine to the coupling agent in the first step, it is possible to increase the number of units in the molecule until, with equimolar amounts, a linear polymer is obtained. By further increasing the amine ratio, compounds containing free terminal amino groups are obtained, a 2:1 ratio of the difunctional amine to the coupling agent giving compounds of formula XI.

R*

? ? (XI)

N ? D ? N*-0 - N - D ? N

i -D i

R' R* *' 20 ?

where the symbols C^, D and R' have the meanings already indicated.

These compounds can then be reacted, for example, with a different coupling agent, of the formula Cl-C^-Cl, and then the reaction can be blocked with a tertiary amine, obtaining, for example, compounds of the formula XII.

RV-v R' R R '

*\ ? '0 10 ? ?

R-N-C'? N? Q-N? C -N- D- ?

N- Ci - N<3-^ R (XII) P i I ?? i ?

R R' R 1 R' R* P \ R (P)

6C1^ By means of such a multistep reaction it is possible to prepare a large number of linear compounds.

It is clear that when any of the symbols R'

?

means a hydrogen atom, the cationic group -N(R') - is an amine salt, not a quaternary ammonium group. When these groups are treated with a base, they lose an H and transform back into secondary amines -NH- or tertiary amines -NR'- where R1 is not hydrogen. This naturally affects the acid-base properties and the water solubility of the molecule. The same considerations apply to terminal groups (R)N- where one or more R groups represent a hydrogen atom. The properties of such compounds generally depend on their chain length, the distance of the quaternary groups in the chain, and the nature of the side groups present. For example, while the compounds are normally water-soluble, it is possible to prepare water-insoluble products by introducing a relatively large number of lipophilic side chains.

0

The anion A is generally made up of the anion of the acid used to form the coupling agent and the halide anion derived from epihalohydrin. When hydrochloric acid is used and the reagent is epichlorohydrin, it is

the anion A is the anion C1. It is naturally possible to exchange the anion for another in the final product. When a 00 0 is present

polyvalent anion, for example SO^ , the symbol A naturally refers to one equivalent of the anion, for example 1/2 SO^ .

Mixtures of products of formula II can be obtained by using mixtures of reagents in one or more reaction steps, after the initial preparation of coupling agent I.

The coupling agent itself, or any compound of formula IX having terminal halogen atoms, can be hydrolyzed with aqueous alkali to the corresponding compounds having terminal hydroxy groups.

The conditions used to prepare the compounds depend on the desired end products and the nature of the starting products used for each step of the desired reaction. In the case of the most reactive amines, the reaction is usually exothermic, even when the coupling agent is in aqueous solution, and one reagent is slowly added to the other at a starting temperature such that the exothermic reaction begins.

The rate of addition of the reagent is used to control the reaction temperature in the usual manner for such cases, employing external cooling if necessary. Initial temperatures are usually between 0 and 100°C, preferably between 20 and 60°C, while the upper limit of the reaction temperature depends on the boiling point of the amine used and the nature of the desired product. In certain cases, it may be necessary to add water to the reaction mass or to

one or both reagents; in other cases, the coupling agent itself may have been prepared in aqueous solution and no further addition of water is necessary. Conversely, certain products must be prepared by reaction in the absence of water. If necessary, organic solvents of appropriate polarity can also be used.

Amines with poor water solubility or poor reactivity usually require quite different reaction conditions and may require careful control of the reaction pH.

A polar solvent is usually used to ensure a homogeneous reaction mixture, with the two reagents usually, but not necessarily, mixed with the solvent at room temperature and then brought to the reaction temperature. In such cases, the reaction temperatures are higher than those used for the more reactive amines, and the reaction is not always exothermic.

The nature of the solvent chosen depends on the nature of the reagents used, the reaction temperature, and the desired properties of the final products. It is clear that the boiling point of the solvent must be equal to or higher than the maximum reaction temperature. These reaction temperatures are generally between 60 and 100°C. Suitable solvents include lower alcohols, such as ethanol, or glycols, such as ethylene glycol and glycol ethers. If desired, the solvent can be distilled off from the reaction mixture before carrying out the reaction, can remain in subsequent steps, or can even be a component of the final formulation.

When the amine has poor water solubility or poor reactivity, it may also be advantageous to use a coupling agent prepared with the minimum amount of water.

The progress of each reaction step can be monitored by observing the disappearance of the amine or functional groups of the coupling agent, or the formation of ions where this occurs during the reaction, for example when the coupling agent contains the reactive site ?chloro??-hydroxy??ethyl in which case the appearance of chloride ions can be observed.

The reaction is continued until the theoretical amount of chloride ions has been released, or until the chloride ion concentration becomes constant.

The hydrolysis of terminal halogen atoms to hydroxy groups can, for example, be carried out in dilute aqueous sodium hydroxide, at temperatures of about 60°C.

Formula II compounds possess surfactant properties that make them suitable, for example, for flocculating and demulsifying oil-in-water or water-in-oil emulsions. Flocculation refers to the initial stage in the breakdown of an emulsion, in which, in the case of an oil-in-water emulsion, the oil droplets coagulate, forming clumps or "flocs" of individual oil droplets. When emulsion breakdown does not progress beyond this stage, the flocs still contain large amounts of water and cannot be used as fuel or oil without further treatment.

The second stage in emulsion breaking is the coalescence of oil droplets in the floc to form increasingly larger droplets, eventually producing a continuous oil phase containing very little water. The transformation of a floc into a continuous oil phase can be facilitated by heating.

The following examples illustrate the present invention without limiting its scope in any way. Parts and percentages are by weight, and temperatures are in degrees Celsius.

Examples 1 to A: Preparation of coupling agents Example 1

To a mixture of 3514 parts demineralized water and 1131 parts (2 moles) of a 60% diethylamine solution, 883 parts of 30% hydrochloric acid are slowly added, maintaining the temperature of the reaction mixture between 35 and 40°C. Then, with continuous cooling and stirring, 2093 parts (3 moles) of epichlorohydrin are slowly added at a rate such that the temperature remains between 35 and 40°C. When the addition of the epichlorohydrin is complete, the mixture is allowed to react for 8 hours at 35 to 40°C and then cooled to 25°C.

?

The resulting 3:2 addition product contains 2 moles of ionic Cl and 2 moles of nonionic reactive chlorine per mole of product. Example 2: Using less water

To 150 parts of a 60% aqueous solution of dimethylamine (2 moles), 104.3 parts of 35% aqueous hydrochloric acid (1 mole) are slowly added, with stirring and cooling to maintain the temperature below 40°C. After cooling the mixture to 35°C, 277.5 parts (3 moles) of epichlorohydrin are added at a rate such that the temperature remains between 35 and 40°C. The product is stirred for 1 hour at 50°C and allowed to stand overnight.

Example 3

To 210 parts of diethanolamine (2 moles), 121.67 parts of 30% aqueous hydrochloric acid (1 mole) are slowly added, with stirring and cooling to maintain the temperature below 40°C. After cooling the mixture to 35°C, 277.5 parts (3 moles) of epichlorohydrin are added at a rate such that the temperature remains between 35 and 40°C. The product is stirred for 1 hour at 50°C and allowed to stand overnight.

Example 4

To 110 parts of demineralized water, 86.3 parts of 36.5% aqueous hydrochloric acid (2 moles) are slowly added at 15°C. Then, slowly, with sufficient cooling to maintain the temperature between 35 and 40°C, 50 parts (1 mole) of tetramethylethylenediamine are added. After cooling the mixture to 25°C, 79.8 parts (2 moles) of epichlorohydrin are added over the course of one hour, maintaining the temperature at 25°C during the addition. The product is then stored overnight at 40°C.

Examples 5 to 20: Blocking reactions

In each of the following examples, 1 mole of the coupling agent is reacted with 2 moles of a monofunctional amine, giving compounds of the formula

? ?

R,N ~ C - NR G

? p 3 2Cr,

In all cases, the reaction is continued until a constant chloride level is observed. Table 1 lists the reagents and reaction conditions. The amount of additional solvent is indicated in parts by weight (amine = 1 part).

Table 1

Agent-of

E.g. copulation Amine Solvent Conditions

No. of the additional R3N reaction example

(C2H5)3N ethanol reflux 5 hours, then (3.7 parts) distill off the ethanol

<g >-NH2 reflux 8 hours:

maintain the pH at 7 by adding 30% NaOH

7 ?(02??0?)3 85-95? / 4 hours

8 HN(C2H4OH)2 60-70? / 4 hours or- 65-75? / 3 hours

10 <5^ CH2NH2 60?/4 hours, then S0?/1 hour, 90?/2.5 hours, 95?/3 hours

11 (n-C4Hg)3N monoethyl ether 85? / 20 hours of ethylene glycol

(0.8 parts)

ethanol

(3.9 parts)

12 dialkylamine gra 110? / 20 hours

knows about coconut oil (the product is a waxy solid (RC)2NH) (see below)

13 di(?-hydroxyethyl) 95? / 10 ?re fatty amine with (the product is a soft, hardened, pasty solid residue of tallow, soluble in ethanol) (see below)

14 <?> 60-70? / 31/2 ?re Es. Agent of

copulazic Amine Solvent Conditions No.

there is no additional reaction R3N

example

15 1 fatty amine ether monoethyl 75? / 1 hour then ?? co of ethylene- 90? / 21 hours (see below) glycol

(0.33 parts)

16 fatty amine dimethy= as e.g. 15 as ex. 15 lata RfN(CH3)2

(see below)

17 1 fatty amine of the o 70? / 1 hour then dimethyl coconut oil 90? / 2 hours lata

R N(CH )

c J i

(see below)

18 3 N(C2H4OH)3 85-95? / 4 hours 19 4 (CH3)3N 90? / 10 hours (aqueous solution

at?:27.5%)

20 4 as ex. 13 95? / 10 hours

The fatty alkyl group of coconut R has the following composition:

Caproyl (C6) 0.5 parts

Caprile (C8) 8.0 parts

Caprile (CIO) 7.0 shares

Lauril (C12) 50.0 parts

Myristile (C14) 18.0 parts

Palmityl (C16) 8.0 parts

Stearyl (C18) 1.5 parts

Oleile (CI8) 6.0 parts

Linoleum (C18) 1.0 part

The fatty alkyl group of hardened tallow R has the following composition:

Myristile (C14) 3.5 parts

Pentadecyl (C15) 0.5 parts

Palmityl (C16) 30.0 parts

Margarile (CI7) 1.5 parts

Stearyl (C18) 62.5 parts

Myristoleyl (C14) 0.5 parts

Palmitoyl (C16) 0.5 parts

Oil (CI8) 1.0 part

The fatty alkyl group has the following composition:

C13 alkyl 70 parts

C15 alkyl 30 parts

where 50 parts are linear and 50 parts are branched, mainly 2-methyl.

Example 21: Blocking with a difunctional amine

The aqueous reaction product prepared in Example 1 (1 mole) is heated to 40 to 50°C and 174 parts (2 moles) of a commercial diamine mixture containing 30 to 36% hexamethylenediamine and 64 to 70% diaminocyclohexane are added dropwise over a period of 90 minutes. The mixture is then stirred for another 4 hours at 50°C or until the analysis shows the theoretical chloride ion concentration.

The product thus obtained corresponds to the formula XI indicated above.

Examples 22 to 30: Reactions to form bridges

In each of the following examples, 2 moles of the coupling agent from Example 1 are reacted with 1 mole of

a nonfunctional amroin, which gives compounds of formula

CI - C - B- C -CI

P P

Table 2 shows the harmines used and the reaction conditions.

Table 2

E.g. Altarina difunctional Solvent Conditions

No. additional reaction

22 H2NCH2CH2NH2 60? / 2 hours

23 RN NH 40?/2 hours, then 60?/l hour 85?/2 hours and 95?/l hour 24 H2NCH2CH2CH2NH2 60? / 2 hours

25 H2N(CH2)6NH2 60? / 1 hour then 80? / 4 hours

26 H2N(CH2)12NH2 60? / 1 hour then 80? / 4 hours

27 HN N-CH CH?NH_ 85? / 4 hours

\_ f 2 2 Z

28 H2NCH2CH2NHCH2CH2NH2 40? / 4 hours then 60 ?/ 2 hours

E.g. Difunctional amine Solvent Conditions No.

additional reaction 29 R methylated ethers indu85-90? /1S ore cNHCHl-CIUICH-LKHL,

strial (1st part)

(R = fatty alkyl of the

c

coconut (see above)

30 1,4-diazobi-Q 50? / 1 hour then cyclo-octane 1 90? / 2 hours

,Examples 31 to 32 Blocking of bridged compounds

In each of the following examples, 1 mole of a bridged compound from Examples 22 to 30 is reacted with 2 moles of a monofunctional amine, giving compounds of the formula

? ? ?

R3N - Cp - B - Cp - NE3 2 Cl

Table 3 shows the reagents and reaction conditions.

Table 3

E.g. Aramine Compound R^N Solvent Conditions No, additional reaction bridges example

31 22 N(CH2CH2OH)3 85-95? / 4 hours 32 23 N(CH2CH2OH)3 95-98? / 3 hours 33 22 HN(CH2CH2OH)2 - 60-70? / 4 hours 34 25 (CH3)2NH 40? / 3 hours then (aqueous solution 70? / 1 hour

Ex. Compound Amine R^N Solvent 'Reaction Conditions No. of additional bridges

of the ex.

35 25 as e.g. 13 50?/1 hour, 80?/7 hours 36 25 60-70?/3.5 hours

37 26 (CH3)2NH

(40? water solution/3 hours then

(60% sa) 70D/1 hour

38 26 <0)-NH2 60?/4 hours then'

80?/l hour 90?/2V2 hours, 95?/3 hours 39 26 N(CH2CH2OH)3 85 -95?/4 hours

40 30 N(CH2CH2OH)3 95?/16 hours

41 30 (Rf)N(CH3)2 isopropanol 90-95?/!6 hours

(4.7 parts)

(R^ = alkyl ethylene glycol, see so- cole

pra) (4.7 parts)

Application examples

Samples of industrial wastewater containing approximately 4% rolling oils, along with other contaminants, are collected. Different doses of demulsifier are added to aliquots of the samples, then all samples are shaken in the same way and left to settle.

The separation or flocculation as well as the clarity of the aqueous phase are then observed and the optimum concentration of the chemicals is recorded.

Application Example A

The wastewater contains 4% of a rolling oil comprising fatty esters and mineral oil, along with other additives, and industrial contaminant residues.

Treatments

Non-ionic products such as polyethylene glycols, ethoxylated alcohols and ethoxylated alkylphenols have only a weak effect, and this only at high application rates.

Aluminum chloride: at high application rates (2000-5000 ppm) it causes rapid flocculation, however it still incorporates water into the flocculate and produces a cloudy aqueous phase.

Aluminum chloride, calcium chloride, and ferric chloride are all ineffective at doses below 1000 ppm.

The product of Example 7 is effective at a dose of 200 ppm and produces, within 24 hours, a homogeneous oil layer and a clear, colourless aqueous phase.

Application Example B

This wastewater contains 4% rolling oil, a mixture of animal fats and mineral oil, with quantities of fatty esters, fatty alcohols, rolling additives, and emulsifiers. This sample is heavily contaminated with industrial waste.

Treatments

Mineral flocculation agents have a very weak effect. The product in Example 8 is effective at a dose of 10,000 ppm. The product in Example 7 is effective at a dose of 5,000 ppm., and the product in Example 31 is effective at a dose of 1,000 ppm.

These products cause a separation that occurs gradually over the course of 2-3 days and yields a homogeneous oil layer and a transparent, pale yellow water layer. Application example C

The sample to be treated is a residual rolling oil from a steel mill and containing 1.03% oil in an aqueous phase.

a) The products of Examples 13, 17 and 19 are effective at a dose between 1000 and 5000 ppm and give a flocculated oil layer and a slightly turbid aqueous layer.

b) The products of Examples 40 and 41 are effective at a dose between 1000 and 5000 ppm and give a very turbid aqueous layer and a reasonably water-free oil layer.

c) The products of Examples 16, 34, 37 and 38 are effective at a dose between 500 and 1000 ppm and give the same results as those given under a).

d) The product of Example 15 is effective at a dose between 500 and 750 ppm and gives a clearer aqueous layer than that obtained under a).

To 14,000 liters of the oil emulsion, 750 ppm of the product from Example 15 are added. The contents of the vessel are stirred for 6 minutes using a pump and then left to stand at 28°C. After 40 hours, the oil content in the aqueous layer is 0.046%. The flocculated oil in the upper layer, when heated to 60°C, yields an oil containing 1.3% water after one hour.

Application Example D

A bitumen oxidation plant produces a distillate containing 60% water and 40% oil, the oil being the continuous phase.

The products of Examples 5, 13, 14, and 19 are effective at a dose between 1000 and 2000 ppm and give an oil layer and a clear, light brown aqueous layer, both at cold temperatures and at the initial distillate temperature (40-50°C). Separation occurs more rapidly at the higher temperatures.

To 29,000 liters of the water-in-oil emulsion containing 62.4% water (pH 9.6), add 50? 1,000 ppm of the product from Example 13. The pH is adjusted to 7 with hydrochloric acid and mixed for 30 minutes using a circulation pump. Water separation begins immediately and is completed after 15 hours of standing. The resulting water-free oil and clear water can be discharged into public sewers.

Claims (1)

Claims 1) The application^as flocculation agents or emulsion breaking agents^of the compounds of formula I ?1 (I) Have you? CH. -CH- :H; N CH5 ? CH? CH..Hal I OH R2 C*3 2 OIH 2 in which Hai means an atom of chlorine or bromine, R and R2 each represent, independently of each other, an alkyl group containing 1 to 5 carbon atoms or a hydroxyalkyl group containing 2 to 5 carbon atoms, Y means an alkylene group containing 2 to 6 carbon atoms, a 2-hydroxy-1,3-propylene group, -C^ CH^NHCONHC^ CH^- or -CH2CH2CH2NHCONHCH2CH2CH2-, ? A represents an anion, and x means an integer between 0 and 7, the symbols Y not necessarily having the same meaning when x means a number greater than 2, of their hydrolysis products and of their reaction products with compounds selected from ammonia, non-polymeric monofunctional amines, and non-polymeric difunctional amines. 2) The application, as flocculation agents or emulsion breaking agents, of the compounds of formula II (formula II see next page) Cp- B Cp- * (II) m in which represents a remainder of formula R111 ?CHj-CH-CHg- 'CH--CH-CHTT 2 ! 2 ?>H ?T R_ R2 OH x in.which R^, ^2? Y and x have the meanings indicated in the claim cation 1, B represents a group of formula III p * p ? _ ;^ D_ ??_ (III) ? I R* R' where the R' groups, which may be identical or different, are selected from hydrogen, alkyl groups containing 1 to 20 atoms carbon mi, alkenyl containing 2 to 20 carbon atoms, hydroxyalkyl containing 2 to 6 carbon atoms, aralkyl and the formula IV groups CH ? CH ? O H (IV) I -R5 where n means a number between 2 and 15?- *-? ?? and the symbols represent each, independently- from each other, a hydrogen atom or a methyl group the, and D represents an alkylene group containing 2 to 20 carbon atoms, a group of formula V CV) ?<CH2)d' -NR -?CH2)T m which and it means a number between 1 and 5, d and f each represent, independently of each other, a number between 2 and 5, and Rg means a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, hydroxyalkyl containing 2 to 6 carbon atoms, or haloalkyl containing 1 to 6 carbon atoms, or a group of formula -(CH ?)? Rr?(CH.)- where g and h mean z g / 2 n ? each, independently of each other, a number between 0 and 3 and represents a 5-7 chain cyclic system that may be saturated or completely or partially unsaturated and that may contain only carbon atoms or a mixture of carbon, oxygen and/or nitrogen atoms, or B represents a group of formula VI CR?) (R') R* (VI) \ I & <CI!2>d N - 0_,q where D', together with the two nitrogen atoms, represents a cyclic system containing one or more 5-7 chain rings that can be saturated, unsaturated or aromatic and that can contain other nitrogen atoms, R? and d have the meanings already indicated, the symbols p and q each mean, independently of each other, 0 or 1; the symbols X each represent, independently of each other, a chlorine or bromine atom, a hydroxy group or a group of formula VII. R ?? Rr ?N ? (VII) wherein the R groups, which may be identical or different, are selected from hydrogen, alkyl groups containing from 1 to 20 carbon atoms, alkenyl groups containing from 2 to 20 carbon atoms, hydroxyalkyl groups containing from 2 to 6 carbon atoms, cycloalkyl groups containing from 3 to 8 carbon atoms, phenyl, aralkyl, alkaryl and the above-mentioned groups of formula IV, or 2 R groups, together with the nitrogen atom to which they are bonded, form a saturated or unsaturated 5-7 chain ring which may contain one or more oxygen atoms or one or more additional nitrogen atoms and which may be substituted by an alkyl group at positions not adjacent to the quaternary nitrogen atom, or 3 R groups, together with the nitrogen atom to which they are bonded, form a polycyclic system which may contain additional oxygen or nitrogen atoms, or represent a system cyclic aromatic which may contain one or more additional nitrogen atoms, in formula group VIII R' R' (Viii) \ N- -?. R' / where R1 and D have the meanings already indicated, k means an integer between 0 and 10, ? A represents an anion, and m means an integer equal to the number of cationic sites in the molecule. 3) A process for flocculation or breaking of an emulsion, characterized in that the emulsion is treated with a compound selected from the compounds of formula I, specified in claim 1, their hydrolysis products and their reaction products with compounds selected from ammonia, non-polymeric monofunctional amines and non-polymeric bifunctional amines. 4) A process according to claim 3, characterized in that the emulsion is treated with a compound of formula II, specified in claim 2. 5) A process according to claim 4, characterized in that the emulsion is treated with a compound of formula IIb X"- C ,? m (Hb) a wherein C^, A and m have the meanings indicated in claim 4 and the symbols X", which may be identical or different, each represent a chlorine or bromine atom or a group of formula H R \ ? R wherein means a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms and represents an alkyl group containing 1 to 4 carbon atoms, the terminal groups being present in the form of an amine salt or free base. 6) A process according to claim 4, characterized in that the emulsion is treated with a compound of formula IIe ? ? ? 0 HjN-D-NH^ Cp-NH2-D-NH- -Cp-NH2-D-NH2 ,? (He) m where 0^, D, k,A and m have the meanings indicated in claim 4. 7) A compound of formula IIa Z- B -? - C - X* ?0? (Ha) J m wherein Cp, B,k,A and m have the meanings indicated in claim 4 and the symbols X' have the meanings indicated for X in claim 4^ under the conditions that, when k = 0, 1) X' is different from a chlorine or bromine atom, 2) when each symbol X* signifies a group of formula VII and when two R groups attached to each of the X* groups represent an alkyl group containing from 1 to 4 carbon atoms, then at least one of the two other R groups present in the molecule is other than hydrogen, and when an R group attached to each of the X1 groups signifies an alkyl group containing 1 to 4 carbon atoms, then at least one of the four other R groups present in the molecule is other than hydrogen, and 3) when each symbol X' represents a group of formula VIII, then in each group X' at least one group R' is different from hydrogen. 8) A compound according to claim 7, wherein both groups X' are identical. 9) A compound according to claim 8, wherein X' represents a group of formula ? R- -N? R- wherein R has the meanings set forth in claim 4. 10) A compound according to claim 9, wherein all the R groups are other than hydrogen. 11) A compound according to claim 10, wherein all the R groups are selected from alkyl groups containing from 1 to 20 carbon atoms and hydroxyalkyl groups containing from 2 to 6 carbon atoms. 12) A compound according to claim 11, wherein all of the R groups are hydroxyethyl groups. 13) A compound according to claim 9, wherein at least one R group in each X' group represents an alkyl group containing from 8 to 18 carbon atoms. 14) A compound according to claim 13, wherein, In each ?' group, one R group represents an alkyl group containing 8 to 18 carbon atoms and the two other R groups each represent a hydrogen atom. 13) A compound according to claim 13? wherein, in each group ?', one R group means an alkyl group containing from 8 to 18 carbon atoms and the two other R groups each represent a methyl or hydroxyethyl group. 16) A compound according to any of claims 7 to 15, wherein, in group C^, the symbols Rx and R? each represent a methyl group, x means 0 or 1, and Y represents a 2-hydroxy-1,3-propylene group. 17) A compound according to any of claims 7 to 16, wherein k) is 0 and B represents a group of formula a) R" ]N? D,L N1?- (a) I R" R" where the symbols R" mean each, independently of the from each other, a hydrogen atom or a methyl group and D" represents an alkylene group containing from 2 to 12 carbon atoms or a group of formula where d' and f each mean, independently of each other, 2 or 3, or B represents a group of formula b) @ - ? ?- (b) c2H4NHr -Jq where q means 0 or 1. 18) A compound according to any of claims 7 to 16, wherein k? 0 and B represents a group of formula <+) 0 -NH_- D?- NH- 2 RI where D" has the meaning indicated in claim 17 and Rm represents an alkyl group containing from 8 to 20 carbon atoms. 19) A compound according to any of claims 7 to 16, wherein k means 0. 20) A compound according to any of claims 7 to 18, wherein k means 1. 21) A process for the preparation of a compound according to claim 19, dependent on claim 9, characterized in that 1 mole of a compound of formula I, specified in claim 1, is reacted in an aqueous medium or in a polar organic solvent with at least 2 moles of ammonia or of a monofunctional amine other than a lower primary or secondary alkylamine. 22) A process for the preparation of a compound according to claim 20, dependent on claim 9, characterized in that 2 moles of a compound of formula I, specified in claim 1, are reacted with 1 mole of a bifunctional amine and the intermediate product is then reacted with at least 2 moles of ammonia or a monofunctional amine, both reaction steps being carried out in an aqueous medium or in a polar organic solvent. 23) A compound according to claim 19 or 20, dependent on claim 9, characterized in that it has been prepared according to the process specified in claim 21 or 22. 24) A process for flocculating or breaking an emulsion, characterised in that the emulsion is treated with a compound specified in any one of claims 7 to 20 and 23.