BE895777A - WATER-SOLUBLE COMPOSITIONS BASED ON CATIONIC HYDROPHILIC POLYMERS AND ANIONIC SURFACTANTS - Google Patents

Description

       

  Water-soluble compositions, base of cationic polymers

  
hydrophilic and anionic surfactants.

  
The present invention relates to cationic hydrophilic polymers which can be used, for example, as flocculating agents. For such uses, it is important that the compositions containing the polymers can be rapidly dispersed or dissolved in water.

  
It has now been discovered that compositions containing an excess of a cationic hydrophilic polymer together with an anionic surfactant, which optionally forms a salt with the cationic polymer, can be readily dispersed or dissolved in water.

  
The present invention therefore relates to a water-soluble composition comprising:
a) a cationic hydrophilic polymer and b) an anionic surfactant, the molar amount of b) not being greater than the molar amount of the cationic monomer units of a).

  
Polymer a) is free of anionic monomer components, and consists either entirely of cationic monomer units

  
or both units of cationic monomers and nonionic monomers. By the term cationic, it is meant that the monomer unit contains a group which can either carry a positive charge or which has basic properties and can be protonized under mild acid conditions. Preferably, such groups are amino or quaternary ammonium groups. Among the suitable polymers a),

  
mention may be made of cationic condensation and addition polymers, for example polyamideamines, polyethyleneimines and polyetheramines, as described for example in patents 3,210,308,

  
3,275,588, 3,329,657, 3,632,559, 3,753,931 and 4,056,610. Preferably, however, the polymer a) is at least partially composed of vinyl addition polymers of vinyl, cationic and optionally nonionic monomers. Preferably, the polymer a) comprises less than 70% by weight of these vinyl addition polymers, preferably at least 90%; the especially preferred polymers a) consist entirely of these vinyl addition polymers.

  
Preferred vinyl monomers are water-soluble monomers, based on esters and amides of acrylic and methacrylic acids, vinyl pyridines, diallylamines, N-vinylpyrrolidones and vinyl esters. Among these cationic monomers, there may be mentioned as preferred types the dialkylaminoalkyl and dialkylaminohydroxyalkyl esters of acrylic and methacrylic acids, and the corresponding trialkylammonium compounds; dialkylaminoalkylic amides of acrylic and methacrylic acids, and the corresponding trialkylammonium compounds, dialkylsulfoniumalkyl esters of acrylic and methacrylic acids; 2- and 4-vinylpyridine and N-alkyl-pyridinium derivatives; the N-alkyl-diallyamines and the corresponding N, N-dialkyl-diallylammonium derivatives.

   Among these compounds, the alkylene groups forming the bridges between the atoms N and 0, 0 and S or N and N, preferably contain from 2 to 4, more advantageously from 2 to 3 carbon atoms, and the alkyl groups on the atoms nitrogen or sulfur preferably contain 1 to

  
4, more preferably 1 or 2 carbon atoms and may be substituted or unsubstituted with phenyl. The phenyl-substituted alkyl group is preferably benzyl; more advantageously, however, the alkyl groups are not substituted.

  
The most preferred cationic monomers are those corresponding to formulas I-VIII.

  

  <EMI ID = 1.1>
 

  

  <EMI ID = 2.1>


  
  <EMI ID = 3.1>

  
R is methyl or ethyl,

  
R is methyl or ethyl,

  
R is hydrogen, methyl or

  
ethyl,

  
X is -0- or -NH-,

  
Y is H or -OH- when X is -0-

  
and H when X is -NH-,

  
n is 0 or 1, provided that when Y is <EMI ID = 4.1>

  
  <EMI ID = 5.1>

  
The object of the invention, however, is A, the latter being the anion of the anionic surfactant b).

  
Particularly preferred cationic monomers are those of formulas I and II, in particular those in which Y is hydrogen and in particular those in which Y is hydrogen, X is -0- and n is zero.

  
Preferred nonionic monomers are acrylamide, methacrylamide, N-vinylpyrrolidone, methyl vinyl ether, ethyl vinyl ether, and the compounds of formula IX.

  

  <EMI ID = 6.1>


  
in which R is as defined above.

  
Among these, acrylamide and methacrylamide, especially acrylamide, are preferred.

  
Preferred cationic polymers a) are copolymers of

  
  <EMI ID = 7.1>

  
methacrylamide and / or acrylamide. In cationic polymers a), the molar quantity of cationic monomer units is preferably at least 5% of the total, preferably 10-80 mole%, in particular 10-40 mole%. It may be advantageous, however, to use a mixture of two cationic polymers of different cationic contents, for example a weak cationic polymer of for example 5-20 mole% of cationic units and a strongly cationic polymer of, for example, 20 -80 mole%, preferably 30-60 mole% of cationic units. A desired cationic content within a defined range can then be obtained by mixing the two polymers

  
in various proportions.

  
The molecular weight (average molecular weight PM) of the polymer is preferably> 100,000, more advantageously & 500,000, in part

  
  <EMI ID = 8.1>

  
example up to 20,000,000.

  
The preferred polymers can be structurally defined as random co-polymers containing recurring units of the following three types:

  

  <EMI ID = 9.1>


  
(1) (2) (3)

  
  <EMI ID = 10.1>

  
is a cationic residue preferably derived from a monomer of form

  
  <EMI ID = 11.1>

  
and Z is a nonionic residue, preferably of formula:

  

  <EMI ID = 12.1>


  
If a 0 and represent the molar proportions of units

  
  <EMI ID = 13.1>

  
The anionic surfactant b) can be any conventional surfactant, having at least one lipophilic hydrocarbon residue and at least one hydrophilic anionic group. Suitable surfactants are described for example in "Surfactant Science Series" (M. Dekker Inc., New York and Basle), vol.7; and "Anionic Surfactants" (ed. W.M. Linfield, 1976), volumes 1 and 2. The lipophilic residue is preferably araliphatic or aliphatic and contains at least 9 carbon atoms, preferably 12-36 carbon atoms. The anionic group can be any conventional acid group, optionally in the form of a salt, for example a carboxylate, a phosphate, a phosphonate, a sulfate and a sulfonate, the latter being the most preferred and the phosphonate the least preferred.

   The molecule may contain polyalkylene glycol ether groups, but these are preferably absent.

  
Preferred classes of anionic surfactants are:
monodi- and triglycerides of sulfated fatty acids, particularly sulfated monoglycerides and sulfated natural oils or fats; sulfated fatty alcohols; alkanols amides of sulfated fatty acids; sulfonated hydrocarbons, especially alkyl sulfonates, olefin sulfonates and alkylaryl sulfonates, especially petroleum sulfonates, and sulfonated aliphatic esters and carboxylic acids, especially esters and Of-sulfo-mono acids -carboxylic and alkyl sulfosuccinates; partially alkylated esters of phosphoric acids; aliphatic carboxylic acids (soaps); and carboxy-methylation products of fatty alcohols, monoglycerides and alkanolamides of fatty acids.

   From the above list, sulfonates, particularly petroleum sulfonates, are preferred.

  
It is preferable that the anionic surfactant is originally present at least partially in the form of a salt with a conventional cation, for example that of an alkali metal, of an alkaline earth metal, ammonium or substituted ammonium (mono-, di-

  
  <EMI ID = 14.1>

  
Preferably, it is in the form of a salt of a polyvalent inorganic cation, Ce 2+ being particularly preferred. In the compositions of the present invention, however, after the polymer a) has been mixed with the surfactant b), the cation of the anionic surfactant can be wholly or partially replaced by cationic units of the polymer. Salts of the surfactant with a polyvalent metal can be prepared in situ by treating the sodium salt of the surfactant with a water-soluble metal salt, for example a formate or a chloride. In the case of calcium, calcium chloride is preferred.

  
The anionic surfactant may be more or less soluble or dispersible in water or may be practically insoluble in water (i.e. it does not give true solutions in water at the concentrations used ; however, it may still be dispersible in water and / or preferably be dispersible or soluble in oil). Preferred anionic surfactants are lipophilic and preferably are such that their sodium salts are soluble in oils. Especially preferred are those which are in the form of salts of these cations (in particular calcium salts) which do not give true solutions in water, but act as a W / O emulsifier.
(water in oil), especially with the oils defined below under section c).

  
The compositions of the invention preferably contain, in addition to a) and b), c) an oil immiscible in water in which the polymer a) is insoluble.

  
When component c) is present, the polymer a) is finely dispersed in the oil c).

  
Component c) can be a single oil or a mixture of oils and can be either natural or synthetic. Among the suitable oils, mention may be made of oils originating from the refining of

  
crude petroleum, vegetable and animal oils, synthetic hydrocarbons, modified paraffins and fatty acid esters.

  
7

  
Preferred representatives of these types of oils are given below:

  
1. Hydrocarbons
1.1. Hydrocarbons from petroleum refining, including:
1.1.1. Petroleum ether, boiling range 65-140 [deg.] C (containing aromatics or being free of aromatics).
1.1.2. White spirits, paint thinners, etc. <EMI ID = 15.1>

  
indicated in Table I below;

  
  <EMI ID = 16.1>

  

  <EMI ID = 17.1>


  
1.1.3. Isoparaffins, boiling range 110-260 [deg.] C;
1.1.4. Paraffin oils (i.e. mineral oils, for example diesel oil, spindle oil, machine oil, cylinder oil, lubrication, petrolatum oil);
1.1.5. petrolatum (preferably mixed with a liquid oil at 20 [deg.] C);
1.2. synthetic hydrocarbons, particularly obtained by Fischer-Tropsch synthesis or by hydrogenation under high pressure of carbon, for example:

  
synthetic petroleum (petrol), boiling range 65-170 [deg.] C Kogasin I boiling range 190-230 [deg.] C Kogasin II boiling range 230-330 [deg.] C

Synthetic paraffin oil boiling range 300-450 [deg.] C

  
1.3. Benzenes and alkylbenzenes, for example toluene xylene and.

  
methyl- ethyl-, trimethyl-, dimethyl-, ethyl- tetram-

  
  <EMI ID = 18.1>

  
2. Animal or vegetable triglycerides, especially olive oil, and peanut oil, cottonseed oil, palm oil, rapeseed oil, sunflower oil, corn oil, castor oil and beef foot oil.

  
3 .. Monoesters of fatty acids, firstly alkyl esters

  
  <EMI ID = 19.1>

  
and isobutyl, stearic, oleic, palmitic and myristic acids, and mixtures thereof.

  
The preferred oils are lower aromatic hydrocarbons and esters of aliphatic fatty acids, in particular the hydrocarbons specified in sections 1.1.2., 1.1.3. and 1.1.4. above, especially white spirits with low aromatics or aromatics-free, isoparaffin and paraffin oils.

  
In a preferred embodiment of the invention, component c) contains a mixture of at least two oils, particularly

  
  <EMI ID = 20.1>

  
that the hydrophilic / lipophilic equilibrium index necessary for an oil / water emulsion (designated in the following by the abbreviation 0 / W-

  
  <EMI ID = 21.1>

  
optimal lipophilic of a hypothetical surfactant that is sufficient to produce a stable oil-in-water emulsion; see for example "Cosmetics, Science and Technology" Wiley, 2nd edition, volume 3, 1974, pp 602-7, or "Emulsion Science" P. Sherman, Academic Press, 1968 pp. 146-7 or "Emulsion; Theory and Practice , P. Becher, Amer. Chem. Soc. Monograph series N [deg.] 162, 2nd edition, 1965.

  
Preferably the O / W-RHLB index of c) is lower than that

  
  <EMI ID = 22.1>

  
the range from 10 to 15; among these oils, mention may be made, for example, of the hydrocarbon oils indicated in the sections 1.1.1., 1.1.2.,
1.1.3. and 1.3. above. Preferred oils c) have O / W-RHLB numbers in the range of 7 to 10; these oils include those specified in sections 1.1.4., 1.1.5., 2. and

  
3. above.

  
Preferably, the compositions according to the invention additionally contain a), b) and preferably c), d) a nonionic lipophilic surfactant.

  
Component d) is preferably lipophilic or oil soluble and may be a single surfactant or a mixture of surfactants. Compound d) works advantageously as a water-in-oil emulsifying agent, that is to say that it is capable of forming a water-in-oil emulsion with at least part of the oil c) in the presence of 'water. The surfactant b) is preferably insoluble in water and has a hydrophilic / lipophilic index less than or equal to 8, more advantageously in the range from 3 to 8, more particularly in the range from 4 to 7. If d) is a mixture, these values apply to the average index of lipophilic-hydrophilic balance of the mixture.

  
Component d) is generally a compound or a mixture of several compounds having at least one lipophilic hydrocarbon residue of at least 9 ,. preferably 9 to 24 carbon atoms and at least one non-ionic hydrophilic residue, which is preferably a mono- or poly-ethylene glycol group, optionally containing propylene glycol units, or else the residue of a polyol, for example , glycerol, mannitol and sorbitol. Among other suitable types,

  
we can cite the hydrophobic Pluronics and Tetronics in which

  
the high propylene oxide content can be considered as

  
the lipophilic residue.

  
Among the specific types of nonionic surfactants, there may be mentioned:

  
The products obtained by adding ethylene oxide (EO) and / or propylene oxide (PO) (preferably EO alone) to aliphatic alcohols, alkylated phenols, fatty acids, fatty acid alkanolamides , partial esters of polyol fatty acids, and vegetable or animal oils or fats; partial fatty acid esters of polyols; EO / PO copolymers having a

  
high PO content (Pluronic type); addition products

  
EO / PO on ethylene diamine, with a high PO content

  
(Tetronic type); diethers of mono- or polyethylene glycols with aliphatic alcohols and alkylated phenols; and diesters of mono- or polyethylene glycols, with aliphatic fatty acids.

  
The preferred number of ethylene oxide units in the adducts of EO to fatty alcohols and alkylated phenols is 1 to 6 and, in the adducts to fatty acids and in diesters of polyalkylene glycols, the number of EO units is preferably from 1 to 10. These numbers are average values and they need not be whole.

  
The partial polyol esters are preferably diesters and more particularly monoesters of aliphatic polyols having

  
3 or more hydroxy groups, in particular glycerol, sorbitol

  
or mannitol.

  
The fatty acid residues can be saturated or unsaturated, (if they are unsaturated, preferably monoethylenically unsaturated) and are preferably acyl groups having from 9 to
24, preferably 12 to 20 carbon atoms, particularly residues of lauric, myristic, stearic, and oleic acids.

  
If an alkyl group is the only lipophilic group, it preferably has from 9 to 24, more advantageously 9 to 18 carbon atoms, and may be a straight or branched chain. In alkylaryl groups, the alkyl group preferably has from 4 to 12 carbon atoms and can also be linear or branched.

  
Particularly preferred surfactants are those of formulas X to XIII.

  

  <EMI ID = 23.1>


  
  <EMI ID = 24.1>

  
Q is the monovalent residue of sorbitol, glycerol or di- or tetraethylene glycol;

  
t is 2-3;

  
r is 1 or 2;

  
k is 3 to 5

  
and m is 4 to 9.

  
The equilibrium hydrophilic / lipophilic indices of nonionic surfactants can be calculated using a standard formula. In order to function as an emulsion or in oil in this system, the hydrophilic / lipophilic index calculated at equilibrium must be greater than 2.5.

  
  <EMI ID = 25.1>

  
oil layer and the surfactant d) are preferably chosen so that the O / W-RHLB index of the oil mixture is as close as possible to the hydrophilic / lipophilic index at equilibrium of d), and in particular is not less than this index.

  
Preferably, the compositions according to the invention contain, in addition to the constituents a), b), c) and preferably d), e) water.

  
The polymer a) and the salts of this polymer with the surfactant b) are hydrophilic and will retain water or will form with water a gel or a sol and in sufficient water will form a true or colloidal solution. The amount of water e) is preferably chosen so that the polymer together with the water disperses finely in the oil. The dispersion may be in the form of a suspension of a wet or water-swollen polymer or of an aqueous polymer gel in oil, or alternatively of an emulsion in a solution of polymer or of sol of aqueous polymer in oil.

  
According to a particular aspect of the invention, the composition contains, in addition to the constituents a) - c), preferably d) and optionally e), f) a polar solvent miscible in oil which is only sparingly soluble in water , does not disperse itself in water, and which does not have any emulsifying properties on its own, but which reduces tension

  
at the water / oil interface.

  
Suitable solvents f) are compounds which have

  
hydrophilic / lipophilic indices at equilibrium, extremely low, but whose molecules are polar enough to direct them at the oil / water interface. Preferred solvents are

  
  <EMI ID = 26.1>

  
or the Pluronics. Examples of suitable solvents that may be mentioned include methyl-isobutyl-carbinol, 2-ethyl-hexanol, isononanol, isodecanol, 2,4,7,9-tetramethyl-5-decyn-4,7 -diol, tributyl phosphate, tri-isobutyl phosphate, phosphate

  
sorting agent (butoxy-ethyl) and Pluronic L101. The presence of f) is desirable in particular if there is little or no water e).

  
Compositions according to the invention can be prepared by mixing a surfactant b), before, during or after the polymerization with the polymer a) and the corresponding monomers, the polymer or the monomers being present in the finely divided form. When a) is something other than a vinyl addition polymer,

  
it is preferable to add the surfactant to the polymer already formed. The polymer must be in finely divided form, for example in the form of an aqueous solution, of an oil dispersion,

  
or, preferably, in the form of a water-in-oil emulsion of an aqueous solution of the polymer in the oil. When the polymer a) .is a vinyl addition polymer, it is advantageous to carry out the polymerization in a water-in-oil emulsion system, and to have at least part of the anionic surfactant b ) present before the polymerization, or at least before the addition of the cationic monomer. After the polymerization, water and / or oil can, if desired, be removed by distillation, and if necessary other additions of one of the components a) -f) can be carried out.

  
Preferably, the vinyl monomers are emulsified under

  
the form of their aqueous solution in at least part of the oil c) in the presence of the anionic surfactant b), and preferably also in the presence of the nonionic lipophilic surfactant d). This water-in-oil emulsion can be formed by adding the vinyl monomers to an already formed water-in-oil emulsion, or else the monomers can be added to an aqueous solution or dispersion of the anionic surfactant b), to which is then added oil and optionally the nonionic surfactant d, and polymerization begins with the addition of a suitable catalyst.

  
The presence of the anionic surfactant in the emulsion or in the oil containing the monomer before the polymerization allows part of the cationic monomers, particularly under acid neutral conditions, to form salts with the surfactants, these salts being less water-soluble and more lipophilic than the monomers themselves. These salts of surfactants and monomers are new and form part of the present invention.

  
Preferred salts correspond to formula XIV.

  

  <EMI ID = 27.1>


  
  <EMI ID = 28.1>

  
  <EMI ID = 29.1>

  

  <EMI ID = 30.1>


  
  <EMI ID = 31.1>

  
  <EMI ID = 32.1>

  
  <EMI ID = 33.1>

  
a petroleum sulfonate.

  
A variant preparation of the compositions according to the invention consists in forming a dispersion containing the polymer a), water e) and the nonionic lipophilic surfactant d) in oil c) in the absence of anionic surfactant b), then adding the surfactant b) to this dispersion. For this alternative method, it is preferable that the anionic surfactant

  
either a sulfonated hydrocarbon soluble in oil and practically insoluble in water, and that the oil is a hydrocarbon oil

  
of the type specified in section 1.1. above, more specifically White Spirit. Preferably, the dispersion is obtained by emulsion polymerization of the monomer solution in oil in the presence of the surfactant d) as an emulsifier, and possibly partial elimination of the water by distillation.

  
The emulsion polymerization, preferably in the presence of anionic surfactant b) can be carried out in a conventional manner (see for example "High Polymers" vol. 9,1955 - "Emulsion Polymerization, Interscience Publishers, NY). Conventional free materials are used to catalyze the polymerization. Among the suitable initiating systems, mention may be made of peroxidized compounds, for example t-butyl hydroperoxide, in combination with redox systems, for example ferric salts, plus thio-sulfate To sequester impurities, it is preferable to add a complexing agent, for example the salts of ethylene diamine-tetra-acetic acid (EDTA).

   The aqueous phase can contain other additives, for example acids, bases or buffering systems for regulating the pH, as well as salts, for example sodium sulphate and calcium chloride.

  
The air in the vicinity of the emulsion is normally replaced by an inert gas and the polymerization begins with the addition of the initiator. The polymerization occurs for example at pH values between 2 and 8, preferably under acidic conditions (pH 2.5-5, preferably 3-4). The water content of the emulsion or in the oil during the polymerization is preferably from 15 to 80% by weight, more advantageously from 30 to 65% by weight, based on the total weight of the emulsion.

  
The polymerization is normally exothermic, and can be carried out under adiabatic or isothermal conditions, but it is preferably carried out partially in an adiabatic manner, that is to say that the temperature is allowed to increase to l 'within certain limits, for example up to 120 [deg.] C, under pressure if necessary. Preferred reaction temperatures are between 30 and 110 [deg.] C. If the reaction mixture contains hydrolysable monomers, for example esters or primary amides, it is necessary to avoid reaction conditions under which significant amounts of hydrolysis products would form.

  
For the water-in-oil emulsion polymerization, it is advantageous to use an oil c) comprising at least 50%, preferably at least 80% by weight of hydrocarbons which should preferably also be and completely aliphatic as possible. The concentration of monomers in the emulsion is not critical, but for economic reasons it is advantageous to work with concentrations as high as practicable. The concentration of surfactants used is adjusted to be sufficient to obtain a stable water-in-oil emulsion in

  
the polymerization conditions.

  
After the polymerization is complete, the water-in-oil emulsion containing the polymer can be treated by adding other amounts of components a) - f) or, if desired, the amount of components c) and / or e) can be reduced by distillation. By such adjustments, the properties of the emulsion, for example its stability and ease of dilution with water, can be influenced and improved. If, in addition to the vinyl addition polymer, other cationic polymers a) are present, these are preferably added after the emulsion polymerization is complete.

  
If component f) is present, it is preferably added after the emulsion polymerization, more advantageously after all the other components have been added. It may be advantageous to mix f) with a little oil c) before the addition.

  
  <EMI ID = 34.1>

  
not already present, can be added after emulsion polymerization, possibly after some, or all of the water has been removed by distillation.

  
According to the invention, very finely divided dispersions can be obtained, even with very small amounts of surfactants.

  
The relative weights of the various constituents of the compositions according to the invention can be represented as follows:
for each 100 parts by weight of polymer a), the composition contains x parts by weight of b), y d c), z of d) u of e) and v of f). The representations 100 for a) and x for b) do not take into account the formation of salt between a) and b); that is to say that the weight of the surfactant and which forms a salt with the polymer does not enter into account in the molecular weight, but remains a part of the weight x.

  
The preferred ranges of x-v are shown in Table II below, the values for each component being independent of each other, unless otherwise indicated. For some applica-

  
  <EMI ID = 35.1>

  
rence less than y. BOARD

TABLE II

  

  <EMI ID = 36.1>


  
The water content (u) can vary between wide limits and in theory it is possible to completely remove the water by distillation by obtaining u = 0. In practice, it is difficult to remove the last traces of water from the polymer, it is also possible to add water in the form of an additional quantity of aqueous polymer solution or in water-in-oil emulsion; so that the water content of the composition can be high. Since it is not economically possible to remove all of the water, u can preferably be 5-300, more preferably 10-200.

  
Preferred compositions contain, per 100 parts by weight of a), 1 to 30 parts of b), 30-400 parts of c), 1 to 80 parts of d), 0 to 300 parts of e) and 0 to 30 parts of f), the weight

  
of f) being less than 1/3 of that of c).

  
Particularly preferred compositions are those in which the weight of each component present is within the

  
range given in the (most advantageous) column of Table II.

  
The oil-containing compositions according to the present invention are dispersions, which can have a wide range

  
viscosity. Brookfield rotational viscosity (measured in

  
an LV viscometer) can vary between 5 cp (pin n [deg.] 2) and 10,000 cp (pin n [deg.] 4), preferably between 50 cp (pin n [deg.] 2) and 5,000 cp
(pin n [deg.] 4). The dispersions are stable and can be stored for long periods of time without change or, if there is a separation between two layers, can be restored to their original form by simple agitation. The compositions of the invention, particularly those containing oil c) have a particularly good dispersion in water and can quickly be diluted with water by stirring or by the use of a conventional dilution apparatus. In a preferred method of dilution, the dispersion is pumped through a nozzle into a stream of water that surrounds the nozzle.

   The water current has a speed greater than that of the dispersion current, and this speed is sufficient to at least partially overcome the internal forces of adhesion and cohesion in the dispersion, but is not sufficient to reduce the size of the polymer molecules. The mixture of product and water is then alternately accelerated in narrow tubes and then decelerated in larger mixing zones until the desired degree of mixing is obtained. Neither sieves nor filters are used in this process from the moment when the water streams and the dispersiori are in contact with each other.

  
A mixing device suitable for implementing the above process comprises at least two cylindrical mixing chambers connected by rigid or flexible piping with a diameter less than or equal to half that of each of the mixing chambers. The first chamber is provided with a tube coaxially mounted for the flow of a stream of water and a second tube, - substantially at right angles to the first, ending in a nozzle situated between the axis and the circumference of the first tube and just above the end of the first tube. Means are provided to pump the dispersion through this second tube. Near the other end of the mixing chamber is an outlet tube leading to

  
the second mixing chamber. The second mixing chamber

  
and any subsequent mixing chamber are each provided with an inlet port and an outlet tube, preferably mounted on the side walls, one in the vicinity of each end of the chamber. Finally, an outlet tube coming from the last mixing chamber leads to the apparatus in which the dilute aqueous dispersion of the composition according to the invention is to be used.

  
A particularly preferred device is illustrated by means of the example of Figures 1 and 2. Figure 1 is a vertical elevation view of a six-chamber mixing device, the upper chamber 1 being shown in cross section. Figure 2

  
is a horizontal cross section along line XX 'in Figure 1.

  
The chambers 1-6 are mounted alternately on the opposite sides of a frame 7 and fixed by the clips 8. The chambers consist of cylindrical piping 9 closed by threaded caps 10 which can be dismantled for cleaning. In the bedroom

  
1, the piping 9 is made of a transparent material to allow direct observation of the mixing process, in the other chambers, it is made of metal.

  
Chamber 1 is provided with a coaxial water supply tube 11,

  
on which a supply tube for dispersion is mounted at right angles

  
12 which ends with a six-hole nozzle 13 so positioned

  
to be completely inside the stream of water delivered by the tube 11. In the cylindrical piping 9, near the end furthest from the tube 11, is an opening 14 leading to

  
a flexible pipe 15 which serves as a connection to a similar opening in the side wall of the chamber 2. From a second opening in the chamber 2, another pipe 16 leads to the chamber 3. The chambers 2 to 6 are all identical construction and

  
are connected, one after the other, by pipes 16-19. Finally, the chamber 6 is provided with a flexible supply pipe 20.

  
In operation, a current of water is passed through

  
the pipe 11 in the chamber 1, and it is allowed to flow until all the chambers are filled and the water comes out through the

  
pipe 20. The Reynolds index of the water flow at the outlet of the

  
pipe 11 is preferably between 25,000 and 75,000, and the fall

  
pressure across the device will be for a medium-sized device with a total volume of 1-100 liters, preferably 0.5 to 2.5 bars, more preferably 0.6 to 1.5 bars.

  
The dispersion is then pumped through the pipe 12 at a rate sufficient to provide the desired concentration of the product. The dispersion passes through the nozzle 13, the size and number of holes of which can vary according to the viscosity of the dispersion, and is rapidly mixed in the stream of water coming from the pipe 11. The mixture passes from the chamber 1 through the narrow pipe 15 in which its flow rate is accelerated, and then in the wide chamber 2 in which its flow rate decreases again. Alternate accelerations and decelerations of flow in successive connecting pipes

  
and the mixing chambers provide complete mixing of the dispersion in water, and the water containing the product is supplied via the hose 20 to the apparatus in which it is to be used.

  
The compositions according to the invention can be very quickly diluted with water and are therefore suitable for use in numerous continuous techniques on an industrial scale, in which cationic polymers are used. Using the mixer described above, completely diluted solutions or dispersions can be obtained without having used a storage tank; the mixer can simply be connected to the equipment in which the diluted product will be used.

  
The compositions can contain very high concentrations of cationic polymers allowing minimal handling of bulky liquids.

  
Not only the concentrated compositions described above; but also partially diluted compositions containing at least 0.01% by weight of polymer a), more advantageously at least 0.1%

  
by weight of a) are part of the field of the present invention. The partially diluted compositions can be further diluted as specified above before use.

  
The compositions of the invention can be used as flocculating agents, particularly as water retention and elimination agents in the paper industry and as flocculating agents for aqueous sludges, particularly aerobic and anaerobic sludges in water purification systems. sewage. They can also be used in other techniques in which cationic polymers are used, for example the flotation of minerals or the recovery of used oils.

  
In the manufacture of paper, the use of the compositions according to the invention can provide a particularly homogeneous sheet formation. The compositions are also notably biodegradable.

  
The following examples illustrate the invention: all parts and percentages are by weight unless otherwise indicated. Examples

  
Emulsifiers used:

  
B sodium salt of sodium monosulfate, PM 440-470

  
(62% solution in mineral oil);

  
B sodium salt of petroleum monosulfate, PM 480

  
(60% solution in mineral oil);

  
B sodium salt of secondary sulfonate of n-alkane, obtained

  
by paraffin sulfoxidation. The alkyl group has the following average composition:

  
  <EMI ID = 37.1>

  
D Sorbitol monooleate, HLB 4.0

  
D, 1: 1 mono- and di-oleates of H (OCH2CH2) 6.50H, HLB 7.0 (value

  
average)

  
Here in the following, HLB stands for hydrophilic / lipophilic index at equilibrium.

  
Oils used:

  
C White. Spirit: free of aromatics, boiling range

  
  <EMI ID = 38.1>

  
  <EMI ID = 39.1>

  
190-250 [deg.] C, average PM 180, aromatic content 0.5%,

  
  <EMI ID = 40.1>

  
with the following properties: density 0.85-0.95, aniline point 70-80 [deg.] C, iodine index 20-30.

  
  <EMI ID = 41.1>

  
density 0.78;

  
  <EMI ID = 42.1>

  
density. 0.87-0.90, acid number 1.12, saponification index 190-200, iodine index 100-110, hydroxy index 40-60;

  
  <EMI ID = 43.1>

  
viscosity (20 [deg.] C.) 30 cp.

  
Solvents used:

  
F triisobutyl phosphate (50% in isobutanol)

  
  <EMI ID = 44.1>

  
  <EMI ID = 45.1>

  
  <EMI ID = 46.1>

  
F5 Pluronic L101 10:90 EO / PO copolymer, P.M.3610

Example 1

  
43.5 parts of emulsifier B are mixed with 800 parts of water, so as to obtain a fine opalescent emulsion. By adding 8.2 parts of calcium chloride, a precipitate of

  
  <EMI ID = 47.1>

  
parts of White Spirit C while stirring, thus obtaining a water-in-oil emulsion which is stabilized by the addition of 99.5 parts

  
  <EMI ID = 48.1>

  
parts of 75% aqueous methacryloyloxy-ethyltrimethylammonium chloride, 454 parts of acrylamide, 1.4 parts of ETDA sodium salt,

  
  <EMI ID = 49.1>

  
after which the pH of the aqueous phase rises to 3.0. The emulsion is heated to 35 ° C. under nitrogen, and an air-free solution of 2.7 parts of sodium thiosulfate in 50 parts of water is added dropwise over 8 hours, the temperature being maintained. at
35-40 [deg.] C by cooling.

  
Polymerization is complete when all of the thiosulfate solution has been added. A fine, stable dispersion of polymer is obtained and has a Brookfield viscosity of 1000 cp (spindle n [deg.] 360 rpm). The product is very easily diluted in water, the maximum viscosity of the 0.5% aqueous dilution with cold water, being reached after only 30-40 seconds. The viscosity of a freshly prepared 1% aqueous dilution is around 500 cp
(Brookfield 3.60 rpm).

Example 2

  
454 parts of acrylamide, 353 parts of methacryloyloxyethyltrimethylammonium chloride, 1.4 parts of disodium EDTA, 0.7 parts of ferric sulfate and 9.8 parts of calcium chloride are added in order to 600 parts of water. The solution thus obtained is then mixed with a solution of 52 parts of emulsifier

  
  <EMI ID = 50.1>

  
by providing a water-in-oil emulsion whose aqueous phase has a pH of 3.0. Under a nitrogen atmosphere, 0.7 parts of t-butyl hydroperoxide are first added and then an air-free solution of 1.1 parts of sodium thiosulfate in 12 parts of water.

  
A strongly exothermic reaction takes place, resulting in a rise in temperature up to 90 [deg.] C even under slight cooling. By cooling, a fine dispersion of polymer is obtained, which is easily diluted in water.

Example 3

  
24 parts of emulsifier B are mixed with 480 parts of water, thus giving a fine opalescent emulsion. To the latter, 564 parts of 75% aqueous methacryloyloxy-ethyltrimethylammonium chloride are added, after which the surfactant salt of the cationic monomer is formed. The following components are then added in the given order, with stirring; namely 408.3 parts of acrylamide, 1.43 part of disodium EDTA, 0.77 part of ferric sulfate

  
  <EMI ID = 51.1>

  
30 parts of emulsifier D2, 4.8 parts of calcium chloride and 0.6 part of t-butyl hydroperoxide.

  
The resulting dispersion is purged with nitrogen and heated to 30 [deg.] C, and then an air-free solution of 2.97 parts of sodium thiosulfate in 42 parts of water is added for 8 hours, temperature rising to 50 [deg.] C. A fine polymer dispersion is obtained, which is easily diluted with water.

  
. Example 4
500 parts of the product of Example 1 are mixed with 10 parts of White Spirit C and 10 parts of emulsifier B and then distilled with a Dean-Starke apparatus at 26 mbar, 40 [deg.] C until 200 parts of water is eliminated. A fine, stable dispersion of polymer is obtained, which, despite its low water content, is easily diluted with water.

Example 5

  
The procedure is as in Example 1 and to the product obtained, 10% of the total weight of the product of Example 3.1 of the United States patent n [deg.] 3,632,559 is added, containing 20% by weight. cationic polymer and 80% water. A stable water-in-oil emulsion is obtained.

Example 6

  
i) Preparation of a polymer dispersion without surfactant

  
active b).

  
454 parts of acrylamide and 353 parts of 75% aqueous methacryloyloxy-ethyltrimethylammonium chloride are dissolved in 800 parts of water, and 1.43 parts of disodium EDTA and 0.72 part of ferric sulfate are added. The pH is adjusted to 3.0 with approximately 0.1 part of 30% caustic soda, then a solution of
143 parts of emulsifier D in 440 parts of White Spirit C is added while stirring vigorously. A milky water-in-oil emulsion is formed, the air of which is carefully removed by stirring by bubbling a stream of nitrogen through the mixture.

  
After addition of 0.67 part of t-butyl hydroperoxide, the mixture is heated to 35 [deg.] C, and a solution of 2.7 parts of sodium thiosulfate in 50 parts of water is added dropwise for 5 hours, the temperature being maintained at 36-38 [deg.] C by cooling. After the addition is complete, the reaction is continued for 2 hours at 35 [deg.] C, and the product is then cooled to room temperature.

  
ii) Addition of surfactant b).

  
An aqueous emulsion containing 20% of B (petroleum sodium sulfcnate) is treated with an excess of calcium chloride, and the precipitate

  
calcium salt collected by filtration, dried under vacuum at 60-70 [deg.] C, is taken up in mineral oil to provide a solution at 30
20 parts of this solution and 20 parts of White Spirit C are added to 200 parts of the suspension prepared in i) above. A viscous product is obtained which, despite its high viscosity, can be quickly diluted with water.

Example 7

  
The calcium salt of emulsifier B is prepared as described

  
  <EMI ID = 52.1>

  
mixture of 80 parts of WhiteSpirit C and 30 parts of mineral oil C3. 25 parts of this solution are added to 200 parts of the suspension prepared in Example 6 i). The resulting mixture is easily diluted with water.

Example 8

  
To 200 parts of the suspension prepared in Example 6 i), 30 parts of a solution containing 14.3% of sulfonate are added

  
  <EMI ID = 53.1>

  
A viscous product is obtained which is easily diluted by adding water.

Example 9

  
To 2210 parts of the polymer emulsion prepared in Example 1, 330 parts of mineral oil C and 330 parts of petrolatum C4 are added, and the mixture is removed under 26 mbar with stirring and then heated to 40 [deg.] C for approximately 6 hours, collecting 860 parts of water in a Dean-Stark trap, the distilled oil being recycled to the distillation mixture. A very fine stable dispersion, slightly viscous, which can be diluted with water approximately as easily as the product of Example 1, is obtained.

Example 10-

  
A dispersion containing 960 parts of water, 816.6 parts of acrylamide, 1128 parts of methacryloyloxy-ethyltrimethylammonium chloride, 75% aqueous, 2.9 parts of disodium EDTA, 1.5 parts of ferric sulfate, 9.1 parts of calcium chloride,

  
  <EMI ID = 54.1>

  
  <EMI ID = 55.1>

  
pH 3.0 and 1.2 parts of t-butyl hydroperoxide are added. The polymerization is carried out under nitrogen by adding 6.5 parts of sodium thiosulfate in 20 parts of water for 8 hours, the temperature

  
  <EMI ID = 56.1>

  
To this product is added 165.7 parts of mineral oil C and
27.7 parts of emulsifier D, then removed by distillation
1186 parts of water at 20-26 mbar and 50 [deg.] C. The resulting fine mobile dispersion is mixed with 157.5 parts of olive oil C and 157.5 parts of 2-ethyl-hexanol (F2). The product is almost instantly diluted in water.

  
Examples 11-13

  
We proceed as in Example 10, replacing F by

  
  <EMI ID = 57.1>

Example 14

  
43.5 parts of emulsifier B are mixed with 834 parts of water to obtain a very fine opalescent emulsion. In order to train

  
  <EMI ID = 58.1>

  
The following constituents are then added while stirring:

  
557 parts of acrylamide, 216 parts of methacryloyloxyethyltrimethylammonium chloride, aqueous at 75%, 1.4 parts of disodium EDTA and 0.7 parts of ferric sulphate, obtaining a turbid solution,

  
  <EMI ID = 59.1>

  
under nitrogen by the addition of 0.7 part of t-butyl hydroperoxide, then 6 parts of a solution of 2.7 parts of sodium thiosulfate in 50 parts of water. The temperature rises to 85 [deg.] C, even when cooling. The resulting dispersion can be quickly diluted with water.

Example 15

  
The procedure is as in Example 14 with the following changes:

  
709 parts of water, 183.3 parts of acrylamide and
714 parts of aqueous cationic monomer; the temperature reaches approximately 43 [deg.] C under adiabatic conditions; and after

  
  <EMI ID = 60.1>

  
  <EMI ID = 61.1>

Example 16

  
The procedure is as in Example 14 with the following changes:

  
  <EMI ID = 62.1>

  
parts of C3; and the temperature is maintained between 35 and 40 [deg.] C.

Example 17

  
43.5 parts of emulsifier B are mixed with 800 parts of water, and to the resulting emulsion is added 8.8 parts of calcium chloride, 363 parts of acrylamide, 124 parts of diallylamine,
353 parts of methacryloyloxy-ethyltrimethylammonium chloride, 75% aqueous, 131 parts of 34% hydrochloric acid to adjust

  
the pH at 3.0, 1.4 parts of disodium EDTA and 0.7 parts of ferric sulphate. a homogeneous monomer solution is formed at which

  
  <EMI ID = 63.1>

  
sodium thiosulfate in 50 parts of water. The temperature during polymerization rises under adiabatic conditions to
65 [deg.] C.

Example 18

  
We proceed as in Example 2 with the following changes:

  
29 parts of emulsifier B are used and the 80 parts of emulsifier D are replaced by a mixture of 49 parts of D

  
  <EMI ID = 64.1>

Example 19

  
We proceed as in Example 17 with the following changes:

  
454 parts of acrylamide are replaced by 363 parts of acrylamide.

  
1-mide + 124 parts of diallylamine; HC1 is not used;

  
  <EMI ID = 65.1>

  
parts of thiosulfate solution replace 16 parts; and the temperature rises in 90 minutes to 90 [deg.] C.

Example 20

  
43.5 parts of emulsifier B are mixed with 600 parts of water. To the solution obtained, 8.2 parts of calcium chloride, 454 parts of acrylamide, 1.4 parts of disodium EDTA are added,

  
  <EMI ID = 66.1>

  
which is polymerized under nitrogen by adding 0.7 part of t-butyl hydroxyperoxide and one part of a solution of 2.7 parts of sodium thiosulfate in 50 parts of water. The polymerization reaction is maintained at a temperature of 60 [deg.] C. When the temperature begins to drop, a solution of 265 parts of methacryloyloxy-ethyltrimethylammonium chloride in 288 parts of water is added dropwise, a subsequent temperature rise which is maintained at 55-60 [deg.] C by cooling. At the end of the addition, the product is stirred for 1 hour at 55 [deg.] C and then cooled to room temperature.

Example 21

  
The procedure is as in Example 15 with the following changes:

  
11 parts of B are used instead of 43.5 parts; 25

  
  <EMI ID = 67.1>

  
3.25 parts of B2 instead of 13 parts; and neither F nor C are added after the polymerization.

Example 22

  
We proceed as in Example 16 with the following changes:

  
  <EMI ID = 68.1>

  
50.00 parts of D are used in place of

  
100 parts;

  
6.5 parts of B are used instead of 13 parts.

Example of dilution

  
A mixing apparatus is used as shown in FIG. 1, comprising 6 chambers each with an internal diameter of
11 cm and a volume of 2.5 1. The connection pipes have an internal diameter of 15 mm and each have a length of 40 cm.

  
In the first mixing chamber, a stream of water of 2000 liters per hour is passed through a nozzle 15 mm in diameter containing a speed of 3.2 m / s. at the nozzle
(Reynolds index 47,000). In the stream of water, 5 l / h of the product of Example 1 is passed by means of a pump operating at a frequency of 50 Hz. The polymer nozzle has 6 holes of 1 mm in diameter, and is equipped with a non-return valve.

  
The diluted product delivered by the mixer is a ready-to-use aqueous solution of the product suitable for use in papermaking.

  
Application example A

  
An aqueous pulp of 2% of the following solution is prepared: 100 parts of pulp bleached with sulphite, 20 parts of kaolin, 3 parts of resin, 2 parts of aluminum sulphate.

  
Four samples (250 ml) of this paste are mixed with respectively 5.10, 15 and 20 ml of an aqueous conditioned dilution with 0.0125% of the product of Example 1 and 750 ml of water. After stirring for 5 sec. at 250 rpm, each mixture is poured into 3 liters of water inside the filling chamber of a Rapid-Kothen sheet forming machine and after 20 s pause, the suction valve is operated to form the sheet. After drying and conditioning, the paper sheet is incinerated and the ash content is measured and then calculated as a percentage of the weight of the load that has been used, providing the percentage of retention. The results are given in Table A below.

TABLE A

  

  <EMI ID = 69.1>


  
Application example B

  
200 parts of an anaerobic slurry suspension having a content of 5% of dry solid are treated with W parts of a solution conditioned with 0.23% of water of the product of Example 1, stirred for 10 s. in a "Triton" agitator at 1000 rpm, then immediately filtered through a fabric filter. For each sample, the volume of filtrate after 30, 60.90, 120 and 180 s. is measured, and the average value of these measurements is calculated. The results are shown in Table B below.

TABLE B

  

  <EMI ID = 70.1>


  
The products of Examples 2-22 can be used analogously in Application Examples A and B.

CLAIMS

  
1. Composition miscible in water, characterized in that it comprises:
a) a cationic hydrophilic polymer and, b) an anionic surfactant, the molar amount of b) being equal to or less than the molar amount of the cationic monomer units of a).


    

Claims (1)

2. Composition according to claim 1, characterized in that component a) comprises at least 70% by weight of vinyl addition polymers, vinyl, cationic and optionally nonionic monomers. 3. Composition according to claim 2, characterized in that that the cationic vinyl monomer is chosen from the compounds of formulas I - VIII  <EMI ID = 71.1>  in which R is H or methyl, R is methyl or ethyl, R is methyl or ethyl, R is hydrogen, methyl or ethyl, X is -0- or -NH- Y is H or -OH, when X is -0- and H when X is -NHn is 0 or 1, provided that when Y is -OH, n = 1 and 1 or when X is -NH- <EMI ID = 72.1> 4. Composition according to claim 2 or 3, characterized in that the nonionic vinyl monomer is chosen from acrylamide, methacrylamide, N-vinylpyrrolidone, methyl vinyl ether, ethyl vinyl ether, and the compounds of formula IX.  <EMI ID = 73.1> wherein R, is as defined in claim 3. 5. Composition according to one of claims 2 to 4, characterized in that the constituent a) is a copolymer of methacryloyloxy-ethyltrimethylammonium salt and of acrylamide. 6. Composition according to any one of the preceding claims, characterized in that component b) is chosen  <EMI ID = 74.1> sulfated fatty alcohols, sulfated fatty alkanolamides; sulfonated hydrocarbons; esters and sulfonated aliphatic carboxylic acids; partial alkyl esters of phosphoric acids; aliphatic carboxylic acids; and carboxymethylation products of fatty alcohols, monoglycerides and alkanolamides of fatty acids. 7. Composition according to claim 6, characterized in that component b) is a petroleum sulfonate. 8. Composition according to claim 7, characterized in that the petroleum sulfonate is present initially in the form of calcium salt. 9. Composition according to any one of the preceding claims, characterized in that it further comprises a) and b), c) an oil immiscible in water in which a) is insoluble. 10. Composition according to claim 9, characterized in that the oil c) is chosen from lower aromatic hydrocarbons and esters of aliphatic fatty acids. 11. Composition according to claim 9 or claim 10, characterized in that the constituent c) comprises a mixture of at least two oils c and c2 chosen so that the hydrophilic / lipophilic index at equilibrium necessary for an oil-in-water emission (0 / W- RHL-B) of c is greater than that of the mixture  <EMI ID = 75.1> 12. Composition according to one of the preceding claims, characterized in that it further comprises a), b), and c), d) a nonionic lipophilic surfactant. 33. Composition according to claim 12, characterized in that d) is either i) one or more of a compound having at least one lipophilic hydrocarbon residue of at least 9 carbon atoms, and at least one non-ionic hydrophilic residue , which is a mono or polyethylene glycol group, optionally containing units of  <EMI ID = 76.1> Hydrophobic Pluronics and Tetronics with high propylene oxide content. 14. Composition according to one of the preceding claims, characterized in that it also contains the components a), b, c, e) water. 15. Composition according to one of the preceding claims, characterized in that it comprises, in addition to the constituents a), b), and c), f) an oil miscible polar solvent, which is only sparingly soluble in water, does not disperse by itself in water, and which has no emulsifying properties on its own, but which reduces the water / oil interfacial surface tension. 16. Composition according to claim 15, characterized in that component f) is chosen from aliphatic alcohols in  <EMI ID = 77.1> 17. Composition according to any one of claims 12 to 16, characterized in that it presents the composition, for each 100 parts by weight of component a), 1 to 30 parts of b), 30 to 400 parts of c), 1 to 80 parts of d), 0 to 300 parts of e) and 0 to 30 parts f), the weight of f) being less than a third of that of c). 18. Composition according to Claim 17, characterized in that it has the composition for each 100 parts by weight of constituent a), 1.5-10 parts of b), 40-200 parts of c), 2-30 parts of d), 2-200 parts of e) and 0-15 parts of f), the weight of f) being less than 1/5 of that of c). 19. Partially diluted composition according to one of the preceding claims, characterized in that it contains at least 0.001% by weight of constituent a). 20. Salt of cationic vinyl monomer and of an ionic surfactant. 21. Salt of cationic vinyl monomer as defined in claim 3 and of an anionic surfactant as defined in claim 7. 22. Formula salt  <EMI ID = 78.1>  <EMI ID = 79.1> claim 3 and A &#65533; is the anion of a hydrocarbon sulfonate. 23. Cationic polymer salt, characterized in that at least part of the cationic groups are associated with the anions of an anionic surfactant. 24. Water in oil emulsion, characterized in that it contains a salt as claimed in any one of claims 21 to 24. 25. Method according to the preparation of a composition as claimed in claim 1, characterized by the stages of mixing of the component b) before, during or after the polymerization with the polymer a) or the corresponding monomers. 26. The method of claim 25, characterized in that a water-in-oil emulsion containing vinyl monomers soluble in water in the aqueous phase is polymerized in the presence of component b). 27. Method according to claim 26, characterized in that that water is removed later by distillation. 28. The method of claim 26 or 27, characterized in that the cationic monomers are at least partly in the form of surfactant salts as claimed in any one of claims 20 to 22. 29. Method for diluting a composition according to any one of claims 1 to 19, characterized in that the composition is pumped through a nozzle in a stream of water which surrounds the nozzle, the stream of water having a speed greater than that of the composition stream, this speed being sufficient to overcome at least in part the internal forces of adhesion and cohesion in the composition, but insufficient to reduce the size of the polymer molecules, and that the mixture of product and water is then accelerated alternately in narrow tubes and then decelerated in larger mixing zones until the desired degree of mixing is achieved. 30. Mixing device suitable for implementing the method according to claim 29, characterized in that it comprises at least two cylindrical mixing chambers connected by rigid or flexible piping with a diameter less than or equal to half that of each of the mixing chambers, the first chamber being provided with a) a tube coaxially mounted for the flow of a stream of water; b) a second tube, disposed substantially at right angles to the first, ending in a nozzle located between the axis and the circumference of the first tube, and just above the end of the first tube; and c), near the other end of the mixing chamber, an outlet tube leading to the second mixing chamber;  the second mixing chamber and its next one each having an inlet and an outlet tube. 31. A method for flocculating an aqueous paste, characterized in that it comprises the stage of adding to the paste an effective amount of a composition according to any one of claims 1 to 19. 32. Process for the production of paper, characterized in that it comprises the addition of a composition according to any one of claims 1 to 19 to the pulp for manufacturing the paper.