FR2530239A1 - - Google Patents

Abstract

THE SUBJECT OF THE INVENTION IS CATIONIC VINYL MONOMERIC SALTS AND SURFACTANTS, WHICH CAN BE INCORPORATED IN WATER-IN-OIL EMULSIONS, FROM WHICH USEFUL COMPOSITIONS ARE PREPARED AS FLOCCULANTS AND RETENTION ADDITIVES IN THE MANUFACTURING .

Description

The present invention relates to cationic hydrophilic polymers

  can be used for example as flocculants For

  such uses, it is important that the compositions containing the poly-

  mothers can be quickly dispersed or dissolved in water.

  It has now been found 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 easily dispersed or dissolved.

in water.

  The subject of the present invention is therefore a solid composition

  in water comprising: a) a cationic hydrophilic polymer and b) an anionic surfactant,

  the molar quantity of b) not being greater than the quantity

  the cationic monomer units of a).

  The polymer a) is free of anionic monomer components, and consists either entirely of monomeric units or both monomeric units and non-monomeric monomers.

  The term cationic means that the monomeric unit

  closes a group that can either carry a positive charge or

  basic properties and can be protonised under 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

  mines, as described for example in the Patents 3,210,308,

  3,275,588, 3,329,657, 3,632,559, 3,753,931 and 4,056,610.

  However, the polymer a} is at least partially

  addition of vinyl addition polymers of vinyl monomers,

  cationic and optionally nonionic. Preferably, the poly-

  mother has> at least 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 the water-soluble monomers based on the esters and amides of acrylic acids and

  methacrylic acid, vinylpyridines, diallylamines, N-vinylpyrrolidines,

  Among these cationic monomers, preferred are the dialkylaminoalkyl and dialkylaminohydroxyalkyl esters of acrylic and methacrylic acids, and the corresponding trialkylammonium compounds; dialkylaminoalkyl amides of acrylic and methacrylic acids, and

  the corresponding trialkylammonium compounds, the dialkyl sulpho

  niumalkyls of acrylic and methacrylic acids; the 2 and the

  4-vinylpyridine and N-alkyl-pyridinium derivatives; the N-alkyl-dial-

  lyamines and the corresponding N, N-dialkyl-diallylammonium derivatives.

  Among these compounds, the alkylene groups forming the bridges between the N and O, O and S or N and N and N atoms, preferably contain from 2 to 4,

  more preferably 2 to 3 carbon atoms, and the alkyl groups

  those on the nitrogen or sulfur atoms preferably contain 1 to

  4, more preferably 1 or 2 carbon atoms and may be

  substituted or unsubstituted with phenyl The alkyl group substituted with phenyl is preferably benzyl; more advantageously,

  however, the alkyl groups are not substituted.

  The most preferred cationic monomers are those corresponding to

laying down in formulas I-VIII.

/ R 2 CH = C Co X (-CH CH CH N I

R 2 2 N 2

  R 3 y CH 2 = C CO -X (CH 2 -d CH-CH 2 N R A II

R 1 R 4

(CH 2 = CH CH 2 -N R III

2 2 2 2

R 2 (CH = CH CH t N A () IV

2 22 A -

R

CH = CH CH = CH CH 2 = CH CH = CH

2 2 2 = 2

ON 94 "and J Aier 5 -'- R AG R 4

VI VI VII VIII

  In the above formulas, R 1 is H or methyl, R 2 is methyl or ethyl, R 3 is methyl or ethyl, R 4 is hydrogen, methyl or ethyl. ethyl, X is -O or -NH-,

Y is H or -OH when X is -O-

  and H when X is -NH-, n is 0 or 1, provided that when Y is

-OH, N = 1

and A is an anion.

  When X is -O and Y is H, N is preferably 0.

  Preferably R 2, R 3 and R 4 are all methyl A G can be

  any conventional anion, preferably a halogen ion (no.

  Cl, Br or I) or an R SOG anion in a preferred form.

to - '4 4

  of the invention, however, Aeest A 1, the latter being the anion

  anionic surfactant b).

  Particularly preferred cationic monomers are those of formulas I and II, especially those in which Y is hydrogen

  and especially those in which Y is hydrogen, X is -O- and N is zero.

  Preferred nonionic monomers are acrylamide, methacrylamide, N-vinylpyrrolidone, methyl vinyl ether,

  ethylvinyl ether, and the compounds of formula IX.

CH 1 3

CH 2 = C CONH CH 2 CO CH IX

I I

R 1 CH 3

  wherein R 1 is as defined above.

  Among these, acrylamide and methacrylamide, in particular

acrylamide, are preferred.

  Preferred cationic polymers a) are copolymers of cationic monomers of formula I or II (Y = H, X = -O-, N is zero), with methacrylamide and / or acrylamide In cationic polymers

  a), the molar amount of cationic monomeric units is preferably

  at least 5% of the total, preferably 10-80 mol%, in particular

  10-40 mole% It may be advantageous, however, to use a

  mixture of two cationic polymers with different cationic contents

  for example, a weak cationic polymer of, for example, 5-20 mol% of cationic units and a highly cationic polymer of

  for example, 20-80 mole%, preferably 30-60 mole% of

  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 preferably> 500,000, in particular

  particular, 1,000,000 PM can be as high as desired, by

example up to 20,000,000.

  The preferred polymers may be structurally defined as random copolymers containing repeating units of the following three types:

R R 1 R.

-CH -C CH -C CH C-

2 2 2

KA KAK z

(1) (2) (3)

  formulas in which R is as defined above, K)

  is a cationic residue preferably derived from a monomer of

  mule II, IV, VII or VIII, A 1 G is the anion of the surfactant b), A 2 'is a nonionic surfactant for example a halogen or R 0403 and Z is a nonionic residue, preferably formula: -CONH 2, -OCH 3, -O C 2 H 5 or -CONHC (CH 3) 2 CH 2 COCH 3 If a, and represent the molar proportions of units (1) (2) and (3) respectively, so that + a + = 100, (a + f) is preferably> 5, more preferably 10-80, in particular 10-40 and a is preferably 15, more preferably 4-10.

  The anionic surfactant b) may be a surfactant

  any conventional active agent having at least one hydrocarbon residue

  lipophilic agent 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 WM Linfield, 1976), Volumes 1 and 2

  phile is preferably araliphatic or aliphatic and contains at least 9 carbon atoms, preferably 12-36 carbon atoms The anionic group may be any conventional acid group, optionally in the form of a salt, for example a carboxylate, a phosphate, a phosphonate, a sulphate and a sulphonate, the latter being the most preferred and the least preferred phosphonate. The molecule may contain polyalkylene glycol ether groups, but these are

preferably absent.

  Preferred classes of anionic surfactants are: sulfated fatty acid mono and triglycerides, particularly

  sulphated monoglycerides and natural oils or fats

  fatées; sulphated fatty alcohols; alkanols amides of sulfated fatty acids; sulfonated hydrocarbons, particularly alkyl sulfonates, olefin sulfonates and alkaryl sulfonates, especially petroleum sulfonates, and sulfonated aliphatic esters and carboxylic acids, particularly esters and α-sulfo-mono acids -carboxylic and alkyl sulfosuccinates; partially alkylated esters of phosphoric acids; acids

  aliphatic carboxylic (soaps); and carboxymethyl

  fatty alcohols, monoglycerides and fatty acid alkanolamides. From the above list, sulfonates, particularly

  Petroleum sulfonates are preferred.

  It is preferred that the anionic surfactant be

  originally at least partially in the form of a salt with a conventional cation, for example that of an alkali metal, a metal

  alkaline earth metal, ammonium or substituted ammonium (mono-, di-

  and triethanol or isopropanolammonium and mono-, di- and triethylammonium, Zn 2 + Al 3 + t Z 4 + Preferably, it is in the form of a salt of a polyvalent inorganic 2 + cation, Ca 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 surfactant

  anionic may be entirely or partially replaced by

  Cationic salts 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. case of calcium, the

calcium chloride is preferred.

  The anionic surfactant may be more or less soluble or dispersible in water or may be substantially insoluble in water (i.e., it does not give true solutions in water

  at the concentrations used; however, it can still be dispersed

  The preferred anionic surfactants are lipophilic and preferably are such that their sodium salts are soluble in oils. Those which are in the form salts of these cations (especially calcium salts) that do not give true solutions in water, but act as emulsifier W / O

  (water in oil), particularly with the oils defined above.

under under heading c).

  The compositions of the invention preferably contain, in addition to a) and b),

  (c) an immiscible oil in water in which the poly-

mother a) is insoluble.

  When component c) is present, polymer a) is fine

dispersed in the oil c) -

  Component c) can be a simple oil or a mixture of oils and can be either natural or synthetic. Suitable oils include oils from crude oil refining, vegetable and animal oils, hydrocarbons and the like.

  synthetics, modified paraffins and fatty acid esters.

  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 ° C (includes

  aromatic or aromatic).

  1.1 2 White spirits, paint thinners etc, ebullition interval

  100-310 ° C., preferably 140 ° -300 ° C., especially those indicated in the following Table I;

TABLE I

  Aromatic content% Free of aromatics 12-19 24-45 -90 Completely aromatic Boiling range, C -270 -210

-310 -

  -260 -310 1.1 3 Isoparaffins, boiling range 110-260 ° C; 1.1 4 Paraffin oils (i.e. mineral oils, by

  example of diesel oil, spindle oil, oil

  the machine, cylinder oil, lubricating oil,

  fication, vaseline oil); 1.1 5 petrolatum (preferably mixed with a liquid oil

at 20 C);

  1.2 synthetic hydrocarbons, particularly obtained by

  the synthesis of Fischer-Tropsch or by hydrogenation under

  high carbon content, eg synthetic oil (gasoline), boiling range 65-170 C Kogasin I boiling range 190230 C Kogasin II boiling range 230-330 C Synthetic paraffin oil boiling range 300- 450 C 1.3 Benzenes and alkylbenzenes, for example toluene, xylene and

  methyl ethyl, trimethyl, dimethyl, ethyl tetramethyl

  thylbenzene and the higher alkylated benzenes, C 6 to C 12 '

  2 Animal or vegetable triglycerides, particularly oil

  olive oil, and peanut oil, cottonseed oil, palm oil, rapeseed oil, sunflower oil,

  corn oil, castor oil and beefstooth oil.

  Fatty acid monoesters, firstly the C 1 to C 4 alkyl esters of C 12 to C 24, preferably C 14 to C 24, fatty acids, particularly the methyl, butyl and isobutyl esters. , stearic, oleic, palmitic and

  myristic, as well as their mixtures.

  The preferred oils are the lower aromatic hydrocarbons

  aliphatic fatty acid esters, including hydro-

  carbides specified in items 1 1 2, 1 1 3 and 1 1 4 above.

  above, especially white spirits weakly aromatic or free

  aromatics, isoparaffin and paraffin oils.

  In a preferred embodiment of the invention, the

  (c) contains a mixture of two or more oils, particularly

  a mixture of an oil c 1) and an oil c 2) chosen so that the hydrophilic / lipophilic balance index necessary for a

  oil / water emulsion (referred to hereinafter by the abbreviation 0 / W-

  RHLB) of c 1) is larger than that of the mixture of c 1) and c 2).

  The O / W-RHLB index of an oil and the hydrophilic balance value

  optimal lipophilicity of a hypothetical surfactant which is suf-

  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", Sherman, Academic Press, 1968 pp 146-7 or "Emulsion, Theory and Practice," P Becher,

  Amer Chem Soc Monograph series N 162, 2nd edition, 1965.

  Preferably the 0 / W-RHLB index of c 2) is lower than that of C 1) Preferred oils C 1) have O / W-RHLB values in the range of 10 to 15; these oils include, for example, the hydrocarbon oils indicated in items 1 1 1, 1 1 2,

  1.1 3 and 1 3 above Preferred oils c 2) have

  0 / W-RHLB dices in the range of 7 to 10; these oils include those specified in items 1 1 4, 1 1 5, 2 and

3 above.

  Preferably, the compositions according to the invention contain, in addition to 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 agents.

  surfactants Compound d) functions avatically as an emulsifying agent

  water-in-oil, that is to say it is capable of forming a water-in-oil emulsion with at least a part of the oil c) in the presence of water The surfactant b) is preferably insoluble in water and has a lower hydrophilic / lipophilic index or

  8, more preferably in the range of 3 to 8, more particularly

  In the range of 4 to 7, if d) is a mixture, these OJ values apply to the lipophilic-hydrophilic equilibrium mean index 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 nonionic hydrophilic residue, which is preferably mono group or

  polyethylene glycol, possibly containing

  pylene glycol, or the residue of a polyol, for example, glycerol

  Among other suitable types are hydrophobic "Pluronic" and "Tetronic" wherein the high propylene oxide content can be considered as

the lipophilic residue.

  Among the specific types of nonionic surfactants that may be mentioned are: Products obtained by addition of ethylene oxide (EO) and / or propylene oxide (PO) (preferably EO alone) to alcohols aliphatics, alkylated phenols, fatty acids, fatty acid alkanolamides, partial esters of polyol fatty acids, and vegetable or animal oils or fats; partial esters of polyol fatty acids; EO / PO copolymers with a high content of PO (of the "Pluronic" t type); EO / PO adducts on ethylene diamine, having a high content of PO ("Tetronic" type); diethers of mono or polyethylene glycols with aliphatic alcohols and alkylated phenols; and diesters of mono or polyethylene glycols, with fatty acids

aliphatic.

  The preferred number of ethylene oxide units in the

  EO additions to fatty alcohols and alkylated phenols are 1 to 6 and in the fatty acid addition products and in the

  di-esters of polyalkylene glycols, the number of EO units is preferably

  from 1 to 10 These numbers are average values and they have

you do not have to be whole.

  The partial esters of polyols are preferably diesters and more particularly aliphatic polyol monoesters having 3 or more hydroxyl groups, in particular glycerol, sorbitol

or mannitol.

  Fatty acid residues may be saturated or unsaturated

  (if unsaturated, preferably monoethylenically

  saturated) and are preferably acyl groups having 9 to 24, preferably 12 to 20 carbon atoms, particularly

  lauric, myristic, stearic, and oleic acid residues.

  If an alkyl group is the only lipophilic group, it presents

  Preferably, from 9 to 24, more preferably 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 may

  also be linear or branched.

  Particularly preferred surfactants are those of

formulas X to XIII.

  R 9 OCH 2 CH 2t OH X (R 8) 8 r 2 2 k XI x O OCH 2 CH 24 OH X

R 10 CO Q XII

Ri CO O - CH 2 CH 2 COR XIII

2 C 2 10

  wherein R 8 is C 4 -C 12 alkyl; R 9 is C 9 -C 8 alkyl or alkenyl; R 10 CO is the acyl residue of a C 2 -C 18 aliphatic fatty acid;

  Q is the monovalent residue of sorbitol, glycerol

  rol 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 hydrophilic / lipophilic indices at equilibrium of the nonionic surfactants can be calculated using a standardized formula In order to function as an emulsion or in

  the oil in this system, the hydrophilic / lipophilic index calculated at

  balance must be greater than 2.5.

  When the oil c) is a mixture of oils c 1) and c 2) the

  The oil mixture and the surfactant d) are preferably chosen so that the O / W-RHLB index of the oil mixture is as close as

  hydrophilic / lipophilic index at equilibrium of d), and in particular

  particular is not inferior to this index.

  Preferably, the compositions according to the invention contain, besides the constituents a), b), c) and preferably d),

e) water.

  The polymer a) and the salts of this polymer with the surfactant

  active b) are hydrophilic and will retain water or form with water a gel or soil and in sufficient water will form a true or colloidal solution The quantity of water e) is preferably chosen so that

  the polymer together with the water is finely dispersed in the oil.

  The dispersion may be in the form of a suspension of a wet or water-swollen polymer or an aqueous polymer gel in the oil, or an emulsion in a polymer or soil solution.

aqueous polymer in the oil.

  According to a particular aspect of the invention, the composition

  contains, in addition to constituents a) c), preferably d) and possibly

  e), f) an oil-miscible polar solvent which is solely

  poorly soluble in water, does not disperse

  even in water, and which has no emul-

  sizing on its own, but reducing 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 orient them at the oil / water interface Preferred solvents are

  C 10 to C 10 aliphatic alcohols, phosphoric acid triesters,

10 '

  Examples of suitable solvents include methyl isobutyl carbinol, 2-ethyl hexanol, isononanol, isodecanol, 2,4,7,9-tetramethyl-5, and the like. -decyn-4,7-diol, tributyl phosphate, tri-isobutyl phosphate, tri (butoxy-ethyl) phosphate and "Pluronie L 101" The presence of f) is

  desirable especially if there is little or no water e).

  Compositions according to the invention can be prepared in

  surfactant b), before, during or after the poly-

  merification with the polymer a) and the corresponding monomers, the

  polymer or monomers being present in the finely divided form

  When a) is 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. , a dispersion in the oil, 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 an addition polymer vinyl, 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 name After the polymerization, water and / or oil may, if desired, be distilled off, and if appropriate

  further additions of one of the components a) -f) can be realized.

  Preferably, the vinyl monomers are emulsified in the form of their aqueous solution in at least a portion of the oil c) in the presence of the anionic surfactant b), and preferably also in the presence of the lipophilic surfactant. non-ionic d) This water-in-oil emulsion can be formed by adding the vinyl monomers to a water-in-oil emulsion already formed, or

  the monomers can be added to a solution or dis-

  aqueous persion of the anionic surfactant b), to which is then added the oil and optionally the nonionic surfactant

  d, and the polymerization begins with the addition of a suitable catalyst.

  prayed. The presence of the anionic surfactant in the emulsion

  or in the oil containing monomer before the polymerization

  Part of the cationic monomers, particularly under neutral to acidic conditions, form salts with surfactants, these salts being less water-soluble and more lipophilic than the monomers themselves. These surfactant salts and

  The monomers are novel and form part of the present invention.

Preferred salts correspond to formula XIV.

R 1

CH 2 = C 1 XIV

  R 1, K and AG are as defined above.

  Preferably R is formula XV

Y R 2

CO X (CH 2 CH -CH CH N R XV

  R 4, X, n, Y, R 2, R 3 and R 4 are defined above, and Y is preferably H, N is preferably zero, and A 0 is the anion of a hydrocarbon sulfonate, more particularly

a petroleum sulphonate.

  An alternative preparation of the compositions according to the invention

  It consists of forming a dispersion containing the polymer a),

  water e) and the nonionic lipophilic surfactant d) in the oil.

  (c) in the absence of anionic surfactant (b), and then to add

  For this alternative method, it is preferable that the anionic surfactant is an oil-soluble and substantially water-insoluble sulfonated hydrocarbon, and that the oil is an oil. hydrocarbon

  of the type specified in item 1 1 above, more particularly

  Preferably, the dispersion is obtained by emulsion polymerization of the monomer solution in the oil.

  in the presence of the surfactant d) as an emulsifier, and optionally

  partially removal of water by distillation.

  The emulsion polymerization, preferably in the presence

  anionic surfactant b) can be carried out in a conventional manner.

  See, for example, "High Polymers" vol 9,1955 "Emulsion Polymerization, Interscience Publishers, N Y.

  classical free radicals are used to catalyze the polymer

  Among the suitable initiator systems are peroxide compounds, for example t-butyl hydroperoxide, in combination with redox systems, for example ferric salts, plus sodium thiosulfate. In order to sequester the impurities, It is preferable to add a complexing agent, for example the salts of ethylene-diamine-tetra-acetic acid (EDTA). The aqueous phase may contain other additives, for example acids, bases or buffer systems to regulate p H, as well as salts, by

  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 starts with the addition of the initial

  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 preferably from 30 to 65% by weight, based on the weight

total emulsion.

  The polymerization is normally exothermic, and can be carried out under adiabatic or isothermal conditions, but it is preferably carried out partially adiabatically,

  that is, the temperature is allowed to increase to the

  within certain limits, for example up to 120 ° C., under pressure if necessary. Preferred reaction temperatures are between 30 and 110 ° C. If the reaction mixture contains hydrolysable monomers, for example primary esters or amides, it is necessary to to avoid reaction conditions in which

  significant amounts of hydrolysis products would be formed.

  For the water-in-oil emulsion polymerization, it is

  it is advantageous to use an oil c) with at least 50%

-2530? 3 9

  at least 80% by weight of hydrocarbons which should be

  preference also and completely aliphatic as possible.

  However, for economic reasons, it is advantageous to work with concentrations as high as practically achievable. The concentration of surfactants used is regulated so as to be sufficient to obtain a sufficient concentration of the surfactant. water-in-oil emulsion stable in

the polymerization conditions.

  After the polymerization is complete, the water emulsion in

  the oil containing the polymer can be treated by addition of

  very large amounts of components a) f) or, if desired, the amount of components c) and / or e) can be reduced by distillation By such settings, the properties of the emulsion, for example its stability and ease of dilution with water, can be influenced and

  If, in addition to the vinyl addition polymer, other poly-

  cationic mothers 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 other components have been added.

  advantageous to mix f) with a little oil c) before the addition.

  If a mixture of oils c 1 and c 2 is used, the polymerization

  It is preferably carried out either in the mixture or in only one, or in a mixture of c 1) with a certain part, but not all of c 2. is not already present, can be added after the emulsion polymerization, possibly after a certain part of, or any

  the water was removed by distillation.

  According to the invention, dispersions can be obtained very finely

  even with very small amounts of surfactants.

  The relative weights of the various constituents of the compositions according to the invention can be represented in the following way: for each time 100 parts by weight of the polymer a), the composition contains x parts by weight of b), y of 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 salt formation between a) and b); i.e., the weight of the surfactant and which forms a salt with the polymer

  does not count for molecular weight, but remains a

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.

  tions, the value of x can be as low as 0.5, v is preferably

less than y.

TABLE II

  (Component a = 100) -Component Value of preferred Most advantageous most advantageous bx 1-30 1-15 1,5-10 cy 30-400 40-200 40-200 dz 0-80 12-30 eu 0-300 1 -300 2-200 fv 0-30 0-30 0-15 (<y / 3) (<y / 3) (<y / 5) The water content (u) can vary within wide limits and in

  theory it is possible to completely remove the water by distillation.

  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 water solution.

  aqueous polymer or emulsion water in oil; so that the

  The water content of the composition can be high As it is not economically feasible to eliminate all water, u can

  preferably 5-300, more preferably 10-200.

  Preferred compositions contain, per 100 parts in

  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

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

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

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

  Compositions containing oil according to the present invention

  These are dispersions, which can have a wide viscosity range. The Brookfield rotational viscosity (measured in an LV viscometer) can vary between 5cp (pin n 2) and 10,000cp (pin NO 4), preferably between 50cp (pin NO 2) and 5000 c P

  (spindle N O 4) The dispersions are stable and can be stored

  for a long period of time without change or, if a separation between two layers occurs, can be restored in their original form by simple agitation. The compositions of the invention, particularly those containing the oil c) possess

  particularly good dispersion in water and can rapidly

  be diluted with water by shaking or by using

  In a preferred method of dilution, the dispersion is pumped through a nozzle in a stream.

  of water that surrounds the nozzle The stream of water has a higher velocity

  than the dispersion current, and this speed is sufficient

  to at least partially overcome the internal forces of

  The product and water mixture is then accelerated alternately in narrow tubes and then decelerated into wider mixing to obtain the desired degree of mixing No sieves or filters are used in this process from the moment when the streams of water

  and the dispersion are in contact with each other.

  A mixing apparatus suitable for implementing the

  above has at least two cylindrical mixing chambers.

  connected by a rigid or flexible pipe of diameter less than or equal to half that of each of the chambers of

  The first chamber is provided with a coaxially

  for the flow of a stream of water and a second tube,

  at right angles to the first, terminating in a nozzle located between the axis and the circumference of the first tube and just above the end of the first tube. Means are provided for pumping the dispersion through this second tube. Near the other end of the mixing chamber, there is an exit 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 inlet port. an outlet tube, preferably mounted on the side walls, one adjacent each end of the chamber Finally, an outlet tube from the last mixing chamber leads to the apparatus in which the dispersion

  diluted aqueous solution of the composition according to the invention must be used.

  A particularly preferred apparatus is illustrated by the example of Figs. 1 and 2. Fig. 1 is a vertical elevational view of a six-chamber mixing apparatus, the upper chamber 1 being shown in cross section. horizontal cross-section along line XX 'of the

figure f.

  The chambers 1-6 are mounted alternately on the opposite sides of a frame 7 and fixed by the fasteners 8.

  consisting of a cylindrical pipe 9 closed by thin hats

  In the chamber 1, the piping 9 is made of a transparent material to allow the direct observation of the mixing process, in the others.

rooms, it is metal.

  The chamber 1 is provided with a water-coaxial feed tube 11, on which is mounted at right angles a dispersion feed pipe 12 which terminates in a six-hole nozzle 13 positioned so as to be located completely within the stream of water delivered by the tube 11 In the cylindrical tubing 9, near the end farthest from the tube 11, there is an opening 14 leading to a hose 15 which serves as a connection to a similar opening

  in the side wall of the chamber 2 From a second or-

  in the chamber 2, another pipe 16 leads to the chamber 3.

  Rooms 2 to 6 are all identical in 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 stream of water is passed through the pipe 1 in the chamber 1, and allowed to flow until all the chambers are filled and the water flows through the pipe 20 L 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 through the device will be for a medium-sized device-

  does not have a total volume of 1-100 liters, preferably 0.5 to 2.5 bars,

253 O 239

  more preferably 0.6 to 1.5 bar.

  The dispersion is then pumped through the pipe 12 at a rate

  sufficient to provide the desired concentration of the product.

  persion passes through the nozzle 13, whose size and number of holes may vary according to the viscosity of the dispersion, and is rapid

  mixed in the stream of water coming from the pipe 11 The

  lange passes from the chamber 1 through the narrow pipe 15 in which

  its flow accelerates, and then in the wide chamber 2 in the-

  the flow rate decreases again The alternating accelerations and decelerations of the flow in the successive connection pipes and the mixing chambers provide a complete mixing of the dispersion in the water, and the water containing the product is delivered

  via the pipe 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 thus suitable for use in

  many continuous techniques at the industrial level, in the

  Cationic Polymers are Used Using the mixer described above, completely dilute solutions or dispersions can be obtained without the use of a storage tank; the mixer can be simply connected to the switchgear

  wherein the diluted product will be used.

  The compositions may contain very high concentrations

  cationic polymers for minimal

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 preferably at least 0.1% by weight of a) are within the scope of this invention. The partially diluted compositions can be further diluted

  as specified above before use.

  The compositions of the invention are useful as flocculating agents, particularly as water retention and removal agents in the paper industry and as flocculants for aqueous sludges, particularly aerobic and anaerobic sludges of water purification systems. They can also be used in other techniques in which cationic polymers

  are used, for example flotation of minerals or the recovery of

used oil.

  In papermaking, the use of the compositions according to the invention can provide a formation of particulate

  The compositions are also remarkably organic.

degradable.

  The following examples illustrate the invention: all the

  percentages and percentages are by weight unless otherwise indicated.

Examples

  Emulsifiers used: B sodium salt of sodium monosulfate, PM 440470 (62% solution in mineral oil) B 2 sodium salt of petroleum monosulfate, PM 480 (60% solution in mineral oil); B 3 sodium n-alkane secondary sulfonate salt, obtained by paraffin sulfoxidation The alkyl group has the following average composition:

  C 13-15 58%; C 16 _ 17 39%; > C 17 <3%; <C 3 <1%

2 O 1

  D C 12 H 25 (OCH 2 CH 2) 2 OH, HLB 6.5

1 1225 2 22

  D 2 C 18 H 35 (OCH 2 CH 2) 30 H, HLB 6.5

  D Sorbitol monooleate, HLB 4.0 D 4 1: 1-mono and di-oleates of H (OCH 2 CH 2) 6.50 H, HLB 7.0 (mean value) Here in the following, HLB means subscript hydrophilic / lipophilic

equilibrium.

  Oils used: C White Spirit: aromatics-free, boiling range 1,193-247 ° C, average MW 173, C 2 White Spirit: weakly flavored, boiling range

  -250 C, average MW 180, aromatic content

  ticks 0.5%, C mineral oil: partially unsaturated mineral oil with the following properties: density 0.85-0.95, aniline point 70-80 C,

iodine number 20-30.

  C 4 petrolatum: freezing point 50-85 C, penetration at the end 160180 at 25 C; C 5 olive oil; C 6 isoparaffin: boiling range 210-260 ° C, point 6 of 88 C aniline, isoparaffin content 80%, density 0.78; C 7 mixture of methyl esters of C 12 to C 20 fatty acids, density 0.87-0.90, acid number 1.12, saponification number 190-200, iodine number 100-110, hydroxy value 40-60; C 8 mineral oil: density 0.85-0.95, 95 C aniline point,

viscosity (20 C) 30 cp.

  Solvents used: F 1 triisobutyl phosphate (50% in isobutanol) F 2 2 ethylhexanol F 3 tri (butoxyethyl) phosphate F 4 2,4,7,9-tetramethyl-5-decyn-4,7-diol F Pluronic L 1 101 10:90 EO / PO copolymer, MW 3610

Example 1

  43.5 parts of emulsifier B 1 are mixed with 800 parts of water, so as to obtain a fine opalescent emulsion. By the addition of 8.2 parts of calcium chloride, a precipitate of calcium salt which is insoluble in water is formed. water of B 1 Finally we add 440

  parts of White Spirit C 1 while shaking, obtaining an emul-

  In this order, 353 parts of 75% aqueous methacryloyloxyethyltrimethylammonium chloride are added, 454 parts of acrylamide are added to the emulsion. 1.4 parts of sodium salt of ETDA, 0.7 parts of ferric sulphate and 0.7 parts of t-butyl hydroperoxide, after which the pH of the aqueous phase is 3.0 L. 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 for 8 hours, the temperature being maintained at

-40 C by cooling.

  The polymerization is complete when all the thiosulphate solution has been added. A fine, stable dispersion of polymer is obtained and has a Brookfield viscosity of 1000 cp (pin n 3.60 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 about 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 to the order of 600 parts of water The solution thus obtained is then mixed with a solution of 52 parts of emulsifier B 1 and 80 parts of emulsifier D 1 in 600 parts of White Spirit C 1, providing a water-in-oil emulsion whose aqueous phase After a nitrogen atmosphere, 0.7 parts of t-butyl hydroperoxide are added first and then a solution free of

  of 1.1 parts of sodium thiosulfate in 12 parts of water.

  There is a strong exothermic reaction, resulting in a rise in temperature up to 90 C even under cooling

  By cooling, a fine dispersion of poly-

  mother, which is easily diluted in water.

Example 3

  24 parts of emulsifier B 1 are mixed with 480 parts of water, thus giving a fine opalescent emulsion to the latter,

  564 parts of methacryloyloxyethyltrimethyl chloride are added

  75% aqueous ammonium, 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 acry-

  lamide, 1.43 parts of disodium EDTA, 0.77 parts of ferric sulphate

  that 480 parts of White Spirit C 1, 30 parts of emulsifier D 1, parts of emulsifier D 2, 4.8 parts of calcium chloride and

  0.6 parts of t-butyl hydroperoxide.

  The resulting dispersion is purged with nitrogen and heated to 30 ° C, and then an air-free solution of 2.97 parts of sodium thiosulfate in 42 parts of water is added for 8 hours.

  hours, the temperature rising to 50 C gives a fine dis-

  Polymer persion, 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 2 and then distilled with a Dean-Starke apparatus at 26 mbar, 40 C until

  200 parts of water is removed.

  stable polymer persion, which, despite its low water content,

  is easily diluted with water.

Example 5

  The procedure is as in Example 1 and the product obtained, 10% of the total weight of the product of Example 3 1 of the US Pat.

  United States of America No. 3,632,559, containing 20% by weight of

  cationic lymere and 80% of water. A water emulsion is obtained in

stable oil.

Example 6

  i) Preparation of a polymer dispersion without surfactant

active b).

  454 parts of acrylamide and 353 parts of 75% aqueous methacryloyloxyethyltrimethylammonium chloride are dissolved in 800 parts of water, and 1.43 parts of disodium EDTA and 0.72 part of ferric sulphate are added. The pH is adjusted to 3 parts. With 0.1 part of 30% sodium hydroxide solution, then a solution of 143 parts of the emulsifier D 1 in 440 parts of White Spirit C 2 is added with vigorous stirring. oil which is carefully flushed through

  stirring by bubbling through the mixture a stream of nitrogen.

  After addition of 0.67 parts of t-butyl hydroperoxide, the

  mixture is heated to 35 C, and a solution of 2.7 parts of thio-

  Sodium sulfate in 50 parts of water is added dropwise

  for 5 hours, the temperature being maintained at 36-38 C by

  chilling After the addition is over, we continue the

  reaction for 2 hours at 35 ° C., and the product is then cooled

di at room temperature.

  ii) Addition of surfactant b) -

  _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

  A 20% aqueous emulsion of B 1 (petroleum sodium sulfonate) is treated with an excess of calcium chloride, and the precipitate of calcium salt collected by filtration, dried under vacuum at 60-70 C,

  is taken up in mineral oil to provide a 30% solution.

  20 parts of this solution and 20 parts of White Spirit C 2 are added to 200 parts of the suspension prepared in i) above. A viscous product is obtained which, in spite of its high viscosity, can

  be quickly diluted with water.

Example 7

  The calcium salt of emulsifier B 3 is prepared as described above for B 1, and -O parts of this salt are dissolved in a

  mixture of 80 parts Whiti Spirit C 2 and 30 parts mineral oil.

  3 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) are added 30 parts of a solution containing 14.3% of sodium petroleum sulphonate B 2, 57.0% of mineral oil C and 28.6%. a

3

  50% solution of tri-isobutyl phosphate in isobutanol (F 1).

  A viscous product is obtained which is easily diluted by the addition of water.

Example 9

  To 2210 parts of the polymer emulsion prepared in the example

  1, 330 parts of C 3 mineral oil and 330 parts of

  trolatum C 4, and the mixture is evacuated under 26 mbar with stirring and then heated at 40 C for about 6 hours, collecting 860 parts

  of water in a Dean-Stark trap, the distilling oil being

  cycled to the distillation mixture A very fine, stable, low-viscosity dispersion is obtained which can be diluted with water

  approximately as easily as the product of Example 1.

Example 10

  A dispersion containing 960 parts of water, 816.6 parts

  of acrylamide, 1128 parts of methacryloyloxyethyl

  trimethylammonium, 75% aqueous, 2.9 parts of disodium EDTA,

2530 39

  1.5 parts of ferric sulphate, 9.1 parts of calcium chloride, 48 parts of emulsifier B 1, 60 parts of emulsifier D 1, 60 parts of emulsifier D 2 and 960 parts of White Spirit C 1 are set at

  H 3.0 and 1.2 part of t-butyl hydroperoxide is added.

  Merification is carried out under nitrogen by adding 6.5 parts of thio-

  sodium sulphate in 20 parts of water for 8 hours, the temperature

  at around 48 ° C despite cooling.

  165.7 parts of C 3 mineral oil and 27.7 parts of D 3 emulsifier are added to this product and then 1186 parts of water are distilled off at 20-26 mbar and 50 C. The resulting product is mixed with 157.5 parts of C 5 olive oil and 157.5 parts of 2-ethyl hexanol (F 2). The product is practically diluted with

instantaneous way in the water.

Examples 11-13

  The procedure is as in Example 10, replacing F 2 with

  equal amounts of F 1, F 3 and F 4, respectively.

Example 14

  43.5 parts of emulsifier B1 are mixed with 834 parts of water to obtain a very fine opalescent emulsion In order to form

  the calcium salt of Bi, 8.2 parts of calcium chloride are added.

  The following constituents are then added while stirring:

  557 parts of acrylamide, 216 parts of methacryloyloxychloride

  75% aqueous ethyltrimethylammonium, 1.4 parts of disodium EDTA and 0.7 part of ferric sulphate, obtaining a turbid solution, to which 400 parts of isoparaffin C 6 is added, 40 parts of C 3 mineral oil, 100 parts of emulsifier D 1 and 13 parts of emulsifier B 2, to obtain an oil-in-water emulsion, which is polymerized under nitrogen by the addition of 0.7 parts 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 C, even when cooling

  The resulting dispersion can be rapidly diluted with

some 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 are used; the temperature reaches approximately 43 C under adiabatic conditions; and after polymerization, 33 parts of Pluronic L 101 (F 5 and 165 parts of C 7 fatty acid esters are added.

Example 16

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

*: 160 parts of C 8 mineral oil are used instead of 40

  parts of C 3; and the temperature is maintained between 35 and 40 C.

Example 17

  43.5 parts of emulsifier B 1 are mixed with 800 parts of water, and the resulting emulsion is added 8.8 parts of calcium chloride, 363 parts of acrylamide, 124 parts of diallylamine,

  353 parts of methacryloyloxyethyltrimethylammonium chloride,

  75% aqueous solution, 131 parts of 34% hydrochloric acid to adjust the pH to 3.0, 1.4 parts of disodium EDTA and 0.7 parts of sulphate

  ferrique Ilse forms a homogeneous monomer solution to which one -

  add 400 parts of White Spirit C 1, 40 parts of mineral oil C and 100 parts of emulsifier D 1 A fine emulsion is formed,

  that it is polymerized under nitrogen by adding 0.7 parts of hydropero-

  t-Butyl x followed by 16 parts of a solution of 2.7 parts

  of sodium thiosulfate in 50 parts of water

  the polymerization rises under adiabatic conditions at

65 C.

Example 18

  The procedure is as in Example 2 with the following changes:

  29 parts of emulsifier B1 are used and the 80 parts of emulsifier D 1 are replaced by a mixture of 49 parts of D 3

and 65 parts of D 4.

Example 19

  The procedure is as in Example 17 with the following changes:

lowing:

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

2 D Y O 3 3 9

  mide + 124 parts of diallylamine; HCl is not used; 54 parts of B 2 replace 100 parts of D; 45 parts of thiosulfate solution replace 16 parts; and the

  temperature rises in 90 minutes at 90 C.

  EXAMPLE 20 43.5 parts of emulsifier B1 are mixed with 600 parts of water 8.2 parts of calcium chloride, 454 parts of acrylamide and 1.4 parts of disodium EDTA are added to the solution obtained. 0.7 parts of ferric sulphate, 400 parts of White Spirit C 1, 40 parts of C 3 mineral oil, 100 parts of emulsifier D 1 and 13 parts of emulsifier B 2 An oil-in-water emulsion is formed 2 'which is polymerized under nitrogen by adding 0.7 part of hydroxypero-

  t-butyloxide and a part of a solution of 2.7 parts of thio-

  Sodium sulfate in 50 parts of water The polymerization reaction

  is maintained at a temperature of 60 C

  To reduce, a solution of 265 parts of inethacryloyloxyethyltrimethylammonium chloride in 288 parts of water is added dropwise to give a subsequent rise in temperature which is maintained at 55-60 ° C by cooling. addition, the product is stirred for 1 hour at 55 ° C. and then cooled to room temperature.

Example 21

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

  : 11 parts of Bl are used instead of 43.5 parts; 25 parts of D 1 are used in place of 100 parts; 3.25 parts B are used in place of 13 parts; and neither F nor C are

2 5 7

added after the polymerization.

Example 22

  The procedure is as in Example 16 with the following changes:

  21.75 parts B instead of 43.5 parts; , 00 parts of D 1 are used in place of parts; 6.5 parts of B are used in place 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 liters.

  an inner diameter of 15 mm and each have a length of 40 cm.

  In the first mixing chamber, a stream of water of 2,000 liters per hour with a velocity of 3.2 m / s at the nozzle (Reynolds index 47,000) is passed through a nozzle 15 mm in diameter. In the stream of water, 5 l / h of the product of Example 1 is passed through a pump operating at a frequency of 50 Hz. The polymer nozzle has 6

  1 mm in diameter, and is equipped with a non-return valve.

  The diluted product delivered by the mixer is an aqueous solution ready for use, of the appropriate product to be used

in the manufacture of paper.

  Application Example A An aqueous paper pulp of 2% of the following solution is prepared: 100 parts of sulfite bleached pulp, 20 parts of

  kaolin, 3 parts resin, 2 parts aluminum sulfate.

  Four samples (250 ml) of this paste are mixed with respectively 5.10, 15 and 20 ml of an aqueous conditioned dilution of 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 Rapidk 8then sheet former and after a pause of 20 s,

  the suction valve is operated to form the sheet.

  After drying and packaging, the paper sheet is incinerated

  the ash content is measured and then calculated as a

  percentage of the weight of the load that has been used,

  the percentage of withholding The results are given in

next table A.

TABLE A

  l Quantity of Density Concentration Retention Dilution Condi-i% Emulsion Added% Polymer Based on the Weight of (Average of 2 Measurements) Dry Paper (%)

| O 8.51 51.1

0.0125 13.31 79.9

0.025 14.34 86.0

0.0375 14.66 88.0

0.05 14.73 88.4

  Application Example B parts of an anaerobic slurry suspension having a content of 5% dry solid are treated with W parts of a solution

  conditioned to 0.23% water of the product of Example 1, stirred 10 s.

  in a "Triton" shaker at 1000 rpm, then immediately filtered through a tissue 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 represented

in the following table B.

TABLE B

  The products of Examples 2-22 can be used analogously in Application Examples A and B. W (parts by weight) Volume of medium filtrate | (parts by volume) I

0 1.5

13 15.3

40.4

17 49.1

19 81.9

Claims (4)

1 Vinyl monomer salt anionic active.   2 Vinyl monomer salt compounds of formulas I VIII CH C-, Co X H CH- R 1 cationic agent and a surfactant cationic chosen from CH CH _N R 2 y R CH = -C - (H CH C Hf-N R 2 CXC 2 2 -3 R R 4 (CH 2 = CH-CH 2 2 -N-R 2 (H 2 = H CH 2 = CH CH 2 12 N - CH 2 = CH   IR 2 c) A GI A III III IV R 4 CH 2 CH C H = CH R 4 VI VI VII VI   In which R 1 is H or methyl, R is methyl or ethyl, R 3 is methyl or ethyl, R 4 is hydrogen, methyl or ethyl, X is -O or -NH- Y is H or -OH, when X is -O and H when X is -NH-   n is 0 or 1, provided that when Y is -OH, N = 1 and 1 or 2 when X is -NH- and A is an anion.   and an anionic surfactant which is a trisulfonate. 3 Formula salt R 1 Y R   1 -15 i e   CH C CO X (CH 2 Y CH CHN N R 3 A 1   R 4 in which R 1, X, n, Y, R 2, R 3 and R 4 are defined as in   Claim 2 and AG is the anion of a hydrocarbon sulfonate.   4 Cationic polymer salt, characterized in that at least a portion of the cationic groups are associated with the anions an anionic surfactant.   Emulsion water in 'oil, characterized in that it   contains a salt as claimed in any one of the dications 2 to 4.