AT397215B - PREPARATIONS CONTAINING POLYMERISAT AND TENSIDES, THEIR PRODUCTION AND USE - Google Patents

Description

AT 397 215 B

Hydrophilic, i. H. Cationic polymers which are soluble or dispersible in water are increasingly being used in industry, for example as flocculants, and rapid dispersibility in or dilution with water of the preparations which contain such polymers is of great importance. It has been found that preparations can be prepared which, in addition to an excess of a cationic, water-soluble polymer, contain an anionic surfactant, optionally in a form bound with salt formation, the polymer being finely distributed in the preparation, and the preparations being readily dispersible in water or are easily dilutable with water.

The invention relates to such preparations, their preparation, their dilution with water and their use, as well as the products obtained by using the preparations and the new monomer and polymer salts.

The invention relates to water-dilutable, polymer, surfactant and oil-containing preparations which are characterized in that they (a) a hydrophilic, cationic polymer, (b) at least one sulfonated hydrocarbon as anionic surfactant, (c) at least one with water immiscible oil in which the polymer is not soluble but finely divided therein, (d) a lipophilic or oil-soluble, non-ionic surfactant and / or (e) water and optionally (f) an oil-miscible, sparingly water-soluble and non-self-dispersible, polar solvent, which alone has no emulsifier properties but lowers the interfacial tension water / oil, the molar fraction of anionic surfactant (b) being no greater than the molar fraction of cationic monomer units of the polymer (a) and where appropriate, the cation of the polymer and the anion of the anionic surfactant are combined to form the salt.

The hydrophilic polymers (a) are cationic, i.e. that is, they are free from anionic monomer components, or they can be obtained by polymerizing exclusively cationic and optionally nonionic monomers.

Any desired cationic addition and condensation polymers are suitable as hydrophilic, cationic polymers (a), e.g. B. the polyamide amine, polyethyleneimine and / or polyetheramine series, as in the. U.S. Patent 3,210,308.3,275,588.3,329,657.3,753,931 and 4,056,510 and U.S. Patent 1,583,363, and / or preferably homo- and copolymers of vinyl-like cationic and optionally non-ionic monomers. As cationic polymers or as cationic monomers here are generally meant both those which already contain cations and those in which the cation is only formed in the presence of water and / or acid, but which are part of anionic monomers.

The polymers (a) occurring in the preparations according to the invention are preferably at least z. T. (aj) cationic homopolymers and / or copolymers of vinyl-like cationic and optionally nonionic monomers, the polymers (a) advantageously consisting mainly of (aj). The proportion (aj) in (a) is preferably at least 70% by weight, in particular at least 90% by weight; particularly preferably (a) consists exclusively of (aj).

Preferred monomers for the preparation of (aj) are vinyl-like, water-soluble monomers, especially those of the acrylic and methacrylic acid series, the acrylic and methacrylic acid series, the vinylpyridine series, the diallylamine series, the N-vinylpyrrolidone series and those of the vinyl ether series.

Preferred representatives of the above-mentioned classes of monomers are among the cationic types (meth) acrylic acid dialkylaminoalkyl ester, (meth) acrylic acid trialkylammonium alkyl ester, (meth) acrylic acid dialkylaminohydroxy alkyl ester, (meth) acrylic acid trialkylammonium hydroxyalkyl, methyl and n-methyldiamide, vinylidene and 2-and 4-n-methyldiamide-n-pyridylidonyldidylidylidyl, and 4-and 4-aminodehydro-nyldiryl, n-and 4-n-di-methyl-n-pyrid, and 2-and 4-n-di-methyl-n-pyrid, and 2-and 4-n-di-methyl-n-pyridine, 2-and 4-n-di-methyl-n-pyridine, and 2-and 4-methyl-alkyl-n-pyrid, N-dialkyldiallylammonium derivatives, (meth) acrylic acid dialkylaminoalkylamides, (meth) acrylic acid trialkylammonium alkylamides and (meth) acrylic acid dialkylsulfonium alkyl esters. The alkylene bridge members (namely between N and O, between O and S and between N and N) advantageously contain 2 to 4, preferably 2 or 3, carbon atoms. The terminal alkyl groups (specifically the substituents on the basic nitrogen or sulfur) advantageously contain 1 to 4, preferably 1 or 2, carbon atoms and can optionally be substituted by phenyl; if they are substituted by phenyl, benzyl is particularly suitable; however, the alkyl radicals are preferably unsubstituted.

Among the cationic monomers mentioned, those of the following formulas are in particular preferred Λ ch2-c-co-o-ch? -Ch2-n * 1 \ -2-0).

AT 397 215 B ® / R2Ae —R ~ \, 3

Cf ^ C-CO-O-Cf ^ -Cf ^ -N -— R 0D, h • * 4 / R2 * 3 CH2 = C-C0-0-CH2-CHOH-CH2-K Rl ^ CH2 = C-C0 -0-CH2-CH0H-CH2-Nq-R3 A0 (IV), li r4 «2 (V), CH25C-C0-NH- (CH2) —HI n \

R _ N R2 (VI), CU2 = C-CO-MH- (CH2) -N -— Rj I n CH2 = CH-CH2 n-r2 (vii). ch2 = ch-ck2 ch2 = ch-ch2s. K CH2iCH-CH2 '/ ^ R2 aq (VIII),

-3-

AT 397 215 B wherein Rj is hydrogen or methyl, Rj is methyl or ethyl, R3 is methyl or ethyl, R4 is hydrogen, methyl or ethyl, A® is a counterion to the ammonium group and n is 2 or 3.

The symbol A® stands for any anion, as is customary with ammonium compounds, advantageously for a halide ion (in particular chloride, bromide or iodide) or for an R4SC> 4® anion. The symbols R2 and R3 preferably each represent methyl; the symbol R4 also preferably represents methyl. In a special embodiment of the invention, Araber also stands for (Aj) © d. that is, for the anion of an anionic, advantageously lipophilic, preferably oil-soluble surfactant, as defined below

Among the cationic monomer units, the (meth) acrylic acid derivatives are generally preferred, especially optionally quaternized (meth) acrylic acid dialkylaminoa] kyl esters and dialkylaminoalky] amides; or among the monomer compounds listed, those of the formulas (I) to (VI), in particular those of the formulas (I), (Π), (V) and (VI) are preferred. Particularly preferred cationic monomers are those of the formulas (I) and (Π).

Preferred representatives of the classes of non-ionic monomers mentioned are those of the following formulas ch2 = c-conh2 (XIII) Ri > -I CH2 = CH-fi (XIV) O ch2 = ch-o-r5 (XV) CH2 = ^ - CO -NH-C (CH3) 2-CH2-CO-CH3 (XVI)

Ri wherein R5 is methyl or ethyl and Rj has the meaning given above

Among the nonionic monomers mentioned, those of the formula (XIII) are particularly preferred, i. H. Methacrylamide and especially acrylamide.

Preferred polymers (aj) are copolymers of cationic monomers of the formula (I) and / or (ü) and nonionic monomers of the formula (XIII).

The polymers (a) or (aj) to be used according to the invention are cationic, i.e. that is, at least some of the corresponding monomers are cationic monomers and any others are nonionic; the proportion of cationic monomer units is advantageously 5 to 100 mol%, preferably 10 to 80 mol%, in particular 10 to 40 mol%. To achieve certain effects or to set certain cation contents, it can also be advantageous to combine two polymers with different cation contents, ie. that is, to use a weaker cationic and a stronger cationic polymer and to blend them together as desired; suitable weaker cationic polymers are those whose proportion of cationic monomer units is advantageously 5 to 20 mol%; Suitable stronger cationic polymers are those whose proportion of cationic monomer units is advantageously 20 to 80 mol%, preferably 30 to 60 mol%

The average molecular weight (weight average) of the polymers can be as high as desired, e.g. B. up to 20,000,000; advantageously they have an average molecular weight > 100,000, preferably > 500,000, particularly preferably > 1,000,000.

Suitable sulfonated hydrocarbons are primarily alkyl sulfonates, olefin sulfonates and alkylarylsulfonates, especially petroleum sulfonates.

The anionic surfactants are advantageously at least z. T. in the form of salts, any conventional cations being considered for salt formation, e.g. B. alkali metal cations (lithium, sodium, potassium), ammonium cations (both unsubstituted ammonium and substituted ammonium, e.g. mono-, di- and tri- (Ci_g-alkyl) ammonium and mono-, di- and tri- (C2_3 -alkanol) ammonium, especially mono-, di- and triethanolammonium], alkaline earth metal cations (magnesium, calcium, strontium and barium) and other polyvalent cations, especially 7s? - +, Al ^ + and Zi ^ +. The anionic surfactants are preferably in Form of the corresponding salts of polyvalent inorganic cations, of which calcium is particularly preferred.

The anionic surfactants can have a more or less pronounced water solubility or dispersibility or can be practically insoluble in water (ie they do not give any real solution in water at the concentrations used, but can still be dispersible in water and / or preferably in oil dispersible or -4-

AT 397 215 B), which essentially depends on the choice of the lipophilic residue and the choice of the cation. Preferred anionic surfactants are the lipophilic ones, preferably those which are oil-soluble in the form of the Na salt, especially those which are in the form of salts of such cations (preferably polyvalent inorganic cations) that they do not give any real solutions in water and with water and with give corresponding oils, especially as defined under c), W / O emulsions, d. H. they have W / O emulsifier character or are W / O emulsifiers.

The above-mentioned anionic surfactants are generally known or can be prepared in a manner known per se. The amine salts and the salts of polyvalent inorganic cations of the anionic surfactants are, for. B. advantageously prepared in situ by reacting the alkali metal salts of these surfactants with water-soluble salts of the corresponding amines or the polyvalent anoiganic cations. Suitable water-soluble salts are essentially salts of stronger inorganic acids (depending on the cation, advantageously sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid) and simple organic carboxylic acids (C i ^ carboxylic acids, primarily formic acid and acetic acid), the sulfates, chlorides being among the amine salts and acetates and among the salts of the polyvalent inorganic cations the formates and especially the chlorides are preferred. Calcium chloride is particularly preferably used.

If the polymers contain cationic monomer units whose counterion is a surfactant anion, their proportion in the polymer molecule is advantageously on average not more than 15 mol%, preferably not more than 10 mol%.

In general, the polymers in the preparations according to the invention contain cationic monomer units and, if appropriate, nonionic monomer units, part of the cationic monomer units containing the anion of the anionic surfactant as counterion to the cation. The polymers can be shown schematically as those which contain the following recurring monomer units: -Ο ι («) (Kat ©) ^ ®) -Q- I (Kat®) (A2 ©) (ß) and optionally -G- (Ύ) wherein (a) and (ß) cationic monomer units, d. i.e., recurring cationic units derived from cationic monomers, (γ) non-ionic monomer units, i.e. recurring, non-ionic units derived from non-ionic monomers, Q the part of the monomer unit which is involved in the backbone, Kat® the bound cationic part and (A f >) a surfactant and (A ^) a non-surfactant anion.

Preferred monomer units (a) and (ß) each correspond to the formulas (<* l) (ßl) -CH2- j3 - (Kat®) ^ ®) Γ -CH2- jD - (Kat $) <A2®) where (cq) and (ß j) or (Kat®) are preferably those radicals such as those derived from the formulas of the formulas (II), (IV), -5-

AT 397 215 B (VI), (Vm), (XI) and (ΧΠ). Af> is preferably the anion of one of the surfactants mentioned above, advantageously of a lipophilic surfactant (as defined above), in particular of one of the sulfonates mentioned. Α3Θ is preferably one of the non-surfactant anions mentioned above, as z. B. is formed by quaternization and / or protonation, preferably halide or I ^ O-SO ^ p.

(A) or, (a ^) particularly preferably stands for or for

(Aai ") (a2) (Aa ^) (" 3> where Aa ^ is the anion of a petroleum sulfonate, in particular a lipophilic petroleum sulfonate. Preferred monomer units (ß) and (ßj) correspond to the formulas -CH2- I1f ® / R2 CO -O-CH2-CH2-N-r3 (Aa2e) (P2) and

(Aa2e) (ß3), where Ao ^ stands for chloride or R40-S03®. Preferred monomer units (γ) are those which correspond to the derivatives of the monomers of the formulas (XE) to (XVI) above, preferably those of the formula -CH2- Γ r co-nh2 (Yl), in particular of the formula -ch2-

fH (Y2) CO-NH2 -6-

AT 397 215 B

Preferred polymers are those which contain or consist of units (04), (βj) and (yj), in particular those which contain or consist of units (α ^, Φ2) and (73).

Component (c) can be either a uniform oil or a mixture of different oils. In general, any oils, such as are used for the production of emulsions and / or dispersions containing water-soluble polymers, are suitable, both natural and synthetic oils. Suitable oils are both oils from the processing of petroleum and vegetable and animal oils (essentially triglycerides); synthetic oils include both synthetic hydrocarbons and modified paraffins (hydrocarbons) and fatty acid esters (primarily triglycerides and monoesters).

Individual, preferred categories of oils are the following; 1. Hydrocarbons 1.1. Hydrocarbons from petroleum processing, primarily special gasoline, which is distilled out of the raw gasoline (boiling range 65-140 ° C) (dearomatized and aromatic-containing types). 1.12. White spirits, white spirit and mineral spirits, (boiling range 100 - 310 ° C, preferably 140 - 300 ° C), especially non-aromatic types (boiling range 100 - 270 ° C, preferably 140 - 250 ° C), fractions with an aromatic content between 12 and 19 % (Boiling range 160-210 ° C), fractions with an aromatic content of 80-90% (boiling range 160-260 ° C), purely aromatic white spirits (boiling range 160-310 ° C). 1.1.3. Aromatic-free hydrocarbons with an isoparaffinic structure (boiling range 110 - 260 ° C) 1.1.4. Paraffin oils (= mineral oils, e.g. diesel oils, spindle oils, machine oils, cylinder oils, lubricating oils and petroleum jelly oils) 1.1.5. Petrolatum (petrolate). 1.2. Synthesis of hydrocarbons, primarily those from Fischer-Tropfsch synthesis or high-pressure coal hydrogenation, in particular synthetic petrolines (boiling range 65 - 170 ° C), Kogasin I (boiling range 190 - 230 ° C), Kogasin II (boiling range 230 - 330 ° C), synthetic paraffin oil (boiling range 300 - 450 ÖC). 1.3. If necessary, alkyl-substituted benzenes, primarily benzene, xylene, toluene, methylethyl and trimethylbenzenes, dimethylethyl and tetramethylbenzenes, as well as higher alkylbenzenes (Cg-C ^ -alkylbenzenes). 2. Natural vegetable or animal triglycerides, especially olive oil, peanut oil, cotton oil, coconut oil, rape oil, sunflower oil, corn oil, castor oil and claw oil. 3. Fatty acid monoesters, primarily C 1.4 alkyl esters of C 12.14, preferably Ci4_24 fatty acids, in particular methyl, butyl and isopropyl esters of stearic acid, oleic acid, palmitic acid and myristic acid and mixtures thereof.

The petrolates are advantageously used in a mixture with oils that are liquid at room temperature.

Among the oils mentioned, the aromatic-free hydrocarbons and the aliphatic fatty acid esters are preferred, in particular the hydrocarbons, including those according to sections 1.1.2.1.1.3 and 1.1.4, and especially aromatic-free and low-aromatic white spirits, isoparaffinic oils (1.1.3 ) and mineral oils (1.1.4) are preferred.

A particular aspect of the invention is that (c) is a mixture of at least two oils, in particular a mixture of an oil (cj) and an oil (C2), which are chosen so that the O / W EHLB value of the oil (C]) is greater than the O / W-EHLB value of the mixture of the oils (c ^) + (C2). O / W-EHLB value means the optimal HLB value of a hypothetical surfactant, which is required for this oil or oil mixture so that a stable oil-in-water emulsion can form (see, for example, &quot; Cosmetics. Science and Technology &quot;, John Wiley and Sons, 2n (* edition, vol. 3 [1974], pages 602-607, or Philip Sherman &quot; Emulsion Science &quot;, Academic Press, London and New York, 1968, pages 146-147, or Paul Becher &quot; Emulsion, Theory and Practice &quot;, 2n ^ edition, 1965, American Chemical Society, Monograph Series, no. 162) Preferably, the O / W EHLB value of the oil (c2) is less than that of the oil (cj).

Preferred oils (c ^) have an O / W EHLB value in the range of 10 to 15; Such oils are among those listed above, especially those mentioned in Sections 1.1.1.1.1.2.1.1.3 and 1.3. Preferred oils (C2) have an O / W EHLB value of 7 to 10; Such oils are among those listed above, in particular those mentioned in Sections 1.1.4.1.1.5.2 and 3.

In addition to the surfactant (b), the preparations according to the invention can also contain nonionic surfactants; this -7-

AT 397 215 B are expediently lipophilic.

The preparations according to the invention therefore advantageously comprise (d) a lipophilic, preferably oil-soluble, nonionic surfactant. This component (d) can be a uniform surfactant or a mixture of lipophilic or oil-soluble, nonionic surfactants. Component (d) is expediently a W / O (water-in-oil) emulsifier, i. that is, a surfactant capable of producing a W / O emulsion with at least a portion of oils (c) in the presence of water. The nonionic surfactants (d) are advantageously water-insoluble or only dispersible in water and, as W / O emulsifiers, advantageously have an HLB value &lt; 8, preferably between 3 and 8; the HLB value is particularly preferably between 4 and 7.

If (d) is a mixture of nonionic lipophilic surfactants, the individual components of this mixture can also have different HLB values, but are then used in such relative amounts that the average HLB value of this surfactant mixture is advantageously &lt; 8, preferably between 3 and 8 and in particular between 4 and 7.

As component (d), i.e. H. Suitable lipophilic, preferably oil-soluble, nonionic surfactants are generally customary compounds, essentially those which contain at least one lipophilic hydrocarbon solid, advantageously having at least 9, preferably 9 to 24 carbon atoms, and at least one nonionic hydrophilic residue, which advantageously contains an optionally Mono or polyethylene glycol residue containing propylene glycol units and / or the residue of a higher polyol (e.g. glycerol, mannitol or sorbitol) These lipophilic or oil-soluble surfactants can also be referred to as hydrophobic surfactants, and among the hydrophobic surfactants also the hydrophobic pluronic types and tetronics in which the high proportion of polypropylene glycol can be referred to as a lipophilic residue. The following categories of nonionic surfactants can be mentioned in particular: mono- or polyoxethylation and / or oxypropylation products of saturated and / or unsaturated, linear and / or branched aliphatic alcohols, of alkylphenols, of fatty acids, of fatty acid alkanolamides, of fatty acid polyol partial esters and of vegetable or animal ones Fats or oils, or corresponding etherification and / or esterification products of mono- and / or polyethylene and / or propylene glycols; Fatty acid polyol partial esters; nonionic ethylene oxide / propylene oxide copolymers with a high proportion of propyleneoxy units (Pluronic types) and ethylene oxide / propylene oxide addition products with ethylenediamine with a high proportion of propyleneoxy units (Tetronic types), which are considered nonionic surfactants due to the high proportion of propyleneoxy units.

The polyol partial esters mentioned are advantageously di- or preferably monoesters of aliphatic polyols with 3 or more hydroxyl groups, primarily glycerol, mannitol or sorbitol.

Preferred nonionic surfactants are generally mono- and / or polyoxethylation products of aliphatic alcohols, of alkylphenols and of aliphatic fatty acids, polyol partial esters of aliphatic fatty acids, mono- and / or diethers of mono- and / or polyethylene glycols with aliphatic alcohols and / or alkylphenols as well Mono- and / or diesters of mono- and / or polyethylene glycols with aliphatic fatty acids.

The fatty acid residues which occur can generally be acyl residues of conventional alkyl carboxylic acids or alkenyl carboxylic acids, monoethylenically unsaturated acids being advantageous as alkenyl carboxylic acids. The alkyl radicals as the only lipophilic radicals [as in the formula (XVII) below] advantageously contain at least 9 carbon atoms, preferably 9 to 24 carbon atoms, in particular 9 to 18 carbon atoms, and can be linear or branched. In the alkylaryl residues, e.g. B. in the rest of formula (a) below, the alkyl radicals advantageously contain 4 to 12 carbon atoms and can also be linear or branched. If the lipophilic residue is the acyl residue of a carboxylic acid, it is advantageously the residue of a fatty acid, essentially an alkyl or alkenyl carboxylic acid, which advantageously contains 9 to 24, preferably 12 to 20 carbon atoms, lauric acid, myristic acid, stearic acid and oleic acid are particularly preferred. The polyethylene glycol derivatives, in particular also the formulas below, are generally average formulas, i.e. H. those in which the specified number of ethyleneoxy units is an average number.

Among the nonionic surfactants mentioned, those of the following formulas are particularly preferred: (XVII)

R6- (0-CH2-CH2) p-0H 5

AT 397 215 B wherein R ^ C9.24 alkyl or alkenyl or a radical of the formula

(a), R7-CO- each the acyl radical of an alkyl or alkenyl carboxylic acid having 12 to 20 carbon atoms, Rg C4_i2-alkyl, X the q-valent radical of glycerol, sorbitol or a mono- or polyethylene glycol of the formula 10 H0- (CH2 -CH2-0) sH (XIX), p 1 to 6, q 1 or 2, or in the case of sorbitol also 3, r 1 or 2 and s 1 to 10, the number and length of the lipophilic radicals and the number of -CH2- CH2-0 grapples are expediently chosen such that the HLB value of the nonionic emulsifier or emulsifier mixture is between 3 and 8, preferably between 4 and 7. Among these, those of the following formulas are preferred (XX),

R9- (0-CH2-CH2) t-0H 20

(0-CH2-CH2) TrOH (XXI),

R10-CO-Y (XXII), R10-CO-O- (CH2-CH2-O) m-CO-R10 (XXIII), 30 where R9 is C9. j g-alkyl or alkenyl, R iQ-CO- the acyl residue of an aliphatic C i2 ig fatty acid, Y - the monovalent residue of sorbitol glycerol or di- to tetraethylene glycol, 12 or 3, k 3 to 5 and m 4 to 9 mean.

The HLB value of the nonionic surfactants can be calculated using a simple known formula, knowing the lipophilic residue, the hydrophilic residue and the number of ethyleneoxy or propyleneoxy units. 35 If the calculated value for a nonionic surfactant is 2.5 or less, then it is no longer considered a W / O emulsifier here

If (c) is a mixture of oils (cj) and (C2), then the surfactants (d) and the oils are advantageously chosen so that the O / W-EHLB ds mixture (cj) + {cj) is as close as possible to the HLB- However, the value of (d) is advantageously not less than this is 40. The preparations according to the invention advantageously also contain (e) water.

The polymers (a) or the polymer salts thereof, which contain the anion of the anionic surfactant as counterion, are hydrophilic, i.e. that is, they can absorb water or form a gel or sol in the presence of water or are at least colloidally soluble in water. The relative amount of water used with the oil (c) and with the emulsifier (d) is generally chosen so that the polymer is dispersed together with the water in the oil (as a suspension of the polymer with absorbed water or water swollen

Polymers or the aqueous polymer gel in the oil, be it as an emulsion of the aqueous polymer sol or the aqueous polymer solution in the oil).

A particular object of the invention is that the preparations additionally (f) contain an oil-miscible, sparingly water-soluble and non-self-dispersible water-based polar solvent which alone does not have 50 emulsifier properties but contains a reduced water / oil interfacial tension.

These solvents are generally polar compounds which have an extremely low HLB value, but are still sufficiently polar to attach to the oil / water interface. These are advantageously water-insoluble, aliphatic alcohols or phosphoric acid triesters or polyalkylene glycols based on block polymers of ethylene and propylene oxide (Pluronic®). The alcohols 55 advantageously contain 5 to 10 carbon atoms per hydroxyl group and the following can be mentioned in particular: methylisobutylcarbinol, 2-ethylhexanol, isononanol, isodecanol and 2,4,7,9-tetramethyl-5-decyn-4,7-diol. Among the phosphoric acid triesters, tributyl phosphate, triisobutyl phosphate and -9-

AT397 215B

Tri- (butoxyethyl) phosphate may be mentioned.

Among Pluronic®, the Pluronic Pluronic L101, an ethylene oxide-propylene oxide copolymer with MW = 3610 and 10% ethylene oxide units, can be mentioned in particular.

The invention further relates to the process for the preparation of the preparations according to the invention, which is characterized in that the anionic surfactant (b) is combined with the polymer (a) or with the corresponding monomers before, during and / or after the polymerization, wherein the polymer or the corresponding monomers are preferably in the finest possible form.

In the case of polymers of non-vinyl-type monomers, it is preferred to add the anionic surfactant to the polymer, which is present in the finest possible form (e.g. as an aqueous solution and / or as a dispersion in oil, preferably as a W / O emulsion of the aqueous polymer solution ) to admit. In the case of polymers of vinyl-like monomers, it is advantageous if the polymerization takes place in a W / O emulsion and at least some of the anionic surfactants are added before the polymerization and / or before the cationic monomer is added.

A particular subject of the invention is the process for the preparation of preparations according to the invention which contain polymers (aj), which is characterized in that the monomers required for the formation of the polymers (aj) are polymerized in the presence of anionic surfactants in a W / O emulsion and if desired, water and / or oil are distilled off and, if appropriate, further additives (a), (b), (c), (d), (e) and / or (f) are added

The vinyl-like monomers are advantageously emulsified in the form of an aqueous solution in the presence of the anionic surfactants and preferably also in the presence of the nonionic, oil-soluble surfactants (d) in at least part of the oil (c), the water-soluble monomers and in particular the cationic monomers in one molar excess over the anionic surfactants. The aqueous phase emulsified in oil may contain further additives, e.g. B. conventional complexing agents, salts and acids and / or bases for pH adjustment. In a preferred process variant, the vinyl-like monomers to be polymerized are added to the submitted W / O emulsion, which already contains anionic surfactant and optionally nonionic surfactant and / or other customary additives, or the vinyl-like monomers to be polymerized are added to the aqueous Dispersion (suspension and / or emulsion) or solution of the anionic surfactant, after which oil and optionally nonionic surfactant and / or other conventional additives can be added. This enables dispersions of the aqueous monomer phase to be produced in oil. Due to the presence of the anionic surfactants in the monomer-containing W / O emulsion, the cationic monomers - or some of them - can be present, especially under neutral to acidic conditions, in the form of less water-soluble, lipophilic surfactant salts, in which the anion of the anionic surfactant acts as a counterion to the cationic monomers acts. A further object of the invention are these salts of cationic vinyl-like monomers, in which the counterion (Aj_) is the anion of an anionic surfactant, preferably a lipophilic or oil-soluble anionic surfactant, they preferably correspond to the formula R) (XXIV). CH2 = C- (Kat ^ (Ai®)

Preferred salts according to the invention are those in which the cation is such as in the formulas (II) (IV) (VI), (VHI), (XI) and (XII); Particularly preferred salts according to the invention are those of sleeves ¢ 1), (IV) and (VI), in which the counterions are those of the above-mentioned anionic surfactants Aj ~, in particular hydrocarbon sulfonates, in particular petroleum sulfonates.

Preferred monomer salts correspond to the formulas r2 CH2 = C - CO - NH - (Co2) n-N®-- R3

Ri ^ R4 (Ap (XXV) CH2 = C - CO - O - NH - CH2CH2-N®d_ r3 R, ** (Ap (XXVI) -10-

AT 397 215 B

The monomer salts according to the invention are preferably prepared by adding an anionic surfactant to an excess of cationic monomers which do not contain a surfactant counterion, in particular as described above. A particular aspect of this subject of the invention are the corresponding W / O emulsions which contain these monomer salts.

A particular embodiment of the production process for the polymer-containing preparations according to the invention consists in that an oily dispersion comprising a hydrophilic, cationic polymer (a), water (s) and a lipophilic or oil-soluble, nonionic surfactant (d), but no anionic surfactant contains, with a lipophilic, preferably oil-soluble, practically water-insoluble, anionic surfactant (bj), where (bj) is a sulfonated hydrocarbon, optionally in salt form, and the oil of the oily dispersion is an oil (C3), <L h. are a water-immiscible hydrocarbon oil, in which the polymer (a) is not soluble, but is finely distributed therein with the water. The polymers (a) here are preferably vinyl-like polymers (aj), as described above. Suitable hydrocarbon oils (C3) are generally those as described in subsection 1.1, of which those according to subsections 1.1.1 to 1.1.4, in particular 1.1.3.1.1.4 and especially white spirits, are preferred.

The polymerization can be carried out in a manner known per se (see, for example, “High Polymers”, vol. 9, 1955 “Emulsion Polymerization”, publisher: Interscience Publishers Inc., New York) and the aqueous system can be used in addition to the contain the usual ingredients, z. B. polymerization initiators (preferably compounds which form free radicals with thermal addition, or a redox system), complexing agents (z. B. Na-EDTA), acids and / or bases for pH adjustment and / or metal salts, eg. B. Na + and / or Ca ^ + salts. After inerting (i.e., after displacing the oxygen with an inert gas) and after adding suitable polymerization initiators, the polymerization takes place. After emulsion polymerization or after bringing together anionic surfactants and cationic polymers, especially after dilution with water, cationic groups in the corresponding salt form can also be present in the polymer. The polymerization is normally exothermic and takes place e.g. B. at pH values between 2 and 8, advantageously under acidic conditions, preferably at pH values between 2.5 and 5, in particular between 3 and 4. The water content of the W / O emulsion during the polymerization is advantageously 15 to 80 % By weight, preferably 30 to 65% by weight, based on the total emulsion). The polymerization can be carried out adiabatically or isothermally, but it is preferably carried out partially adiabatically, i. that is, the temperature is allowed to rise to a limited extent by metered addition of the initiator and / or by cooling the reaction mixture, advantageously to values <120 ° C., if appropriate under pressure. The procedure is preferably between 30 and 110 ° C. If the mixture to be polymerized contains hydrolyzable monomers (in particular esters or primary amides), such reaction conditions are expediently chosen; that hydrolysis to the undesirable acids is avoided as much as possible.

With the surfactants to be used according to the invention, very finely divided dispersions can be achieved even with relatively little surfactant. The emulsion polymerization enables very high molecular weights of the polymers to be achieved, so that a very broad spectrum of molecular weights of the polymers can be available, which also allows the preparations according to the invention to be used very widely.

The emulsion polymerization is advantageously carried out in the presence of at least some of the oils (c). Oils in which at least a part, preferably at least 50% by weight, particularly preferably at least 80% by weight, are hydrocarbons are advantageously used for the emulsion polymerization, aliphatic hydrocarbons being preferred. The relative amounts of water and oil, as well as the concentration of the aqueous monomer solution can vary widely, the procedure being preferably concentrated for economic reasons. The W / O emulsion to be polymerized contains at least part of the surfactants (b) [preferably (b ')] and / or (d) which is sufficient to produce a W / O emulsion which is sufficiently stable for the polymerization. After the polymerization, the polymer-containing W / O emulsion obtained can be mixed with further additives, for. B. with further components (a), (b), (c), (d) and / or (e) and / or with component (f), and / or the content of components (c) and / or (e), e.g. B. be reduced by distillation. These additional modifications of the polymer-containing W / O emulsions can affect the properties of the preparations, e.g. B. affect their stability and / or their dilutability with water, in particular improve. If the preparation should also contain other polymers (a) in addition to polymer (aj), the latter are preferably added after emulsion polymerization has taken place.

If the preparation should also contain component (f), then this is advantageously added to the preparation as the last, or after emulsion polymerization has taken place. Conveniently, (f) is used in a form prediluted with a little oil (c). If desired, however, larger amounts of oil (c) can also be used and / or further additives (a), (b), (d) and / or optionally together with (f) or with its solution in oil (c) (e) added to the preparation.

If the preparation is to contain a mixture of oils (cl) and (03), then the emulsion is polymerized -11-

AT397 215 B advantageous in oil (cj), which may contain (cj). If necessary, the oil (¢ 2) or the remaining part of the oil (C2) can be added after the emulsion polymerization has taken place, if appropriate after distilling off the water or most of the water.

The quantitative composition of the preferred preparations according to the invention and obtainable as described above can advantageously be schematized as follows; the preparation contains per 100 parts by weight of component (a) x parts by weight of component (b), y parts by weight of component (c), z parts by weight of component (d), u parts by weight of component (e) and v parts by weight of component (f) .

The concentrations x and z preferably correspond at least to those which are necessary so that the aqueous monomer-containing dispersion remains sufficiently stable during the polymerization, x is advantageously at least 0.5, primarily Ibis 30, preferably 1 to 15 and in particular 1.5 to 10 (a) and (b) refer to the respective components without taking into account a corresponding salt formation in the numbers 100 for (a) and x for (b), but should also include the possible salt formation of (a) + (b), z is advantageously 0 to 80, preferably 1 to 80 and particularly preferably 2 to 30. The preparations according to the invention are advantageously oil-containing and y is preferably 30 to 400, particularly preferably 40 to 200. The water content can vary greatly and is e.g. T. also from the content of oil, d. H. dependent on y, to that extent; than the preparations according to the invention, in the oil-containing form which has not yet been diluted with water, if they contain water, predominantly in the discontinuous phase. That is, oil is the continuous phase and the water-containing phase is dispersed or emulsified therein. After the (inverse) emulsion polymerization, the water can be distilled off, advantageously azeotropically, and in theory all the water can be distilled off, i. that is, up to u = 0, but this is practically not preferred since it is difficult to completely distill off the residual water which swells the polymer. On the other hand, the polymer-containing W / O emulsion may also contain water, e.g. B. also in the form of a further W / O emulsion or an aqueous solution of a polymer (a), so that the water content of the preparation can also be relatively high, u is advantageously 0 to 300, preferably 1 to 300 and particularly preferably 2 to 200. From an economic point of view, it is preferred not to distill off all the water, and the water content u is advantageously 5 to 300, preferably 10 to 200.

In order to further facilitate the dispersibility of the polymer in water by dilution, it may be advantageous to add component (f) to the preparation, with (f) being used in the smallest possible amounts, in particular in amounts smaller than y [the Component (f) is dissolved in component (c)]; v is advantageously 0 to 30, preferably 0 to 15.

The preparations according to the invention advantageously have the following composition: per 100 parts (a) x = 1 - 30 y = 30 - 400 z = 1 - 80 u = 0 - 300 v ss 0 - 30, (where v <y / 3 )

A particularly preferred composition of the preparations according to the invention is as follows: per 100 parts (a) x = x '= 1.5 -10 y = y' = 40 - 200 z = z '= 2 - 30 u = u' = 2 - 200 v = ν '= 0 -15 and ν' &lt; y '/ 5

The oil-containing preparations according to the invention are dispersions which can have very different viscosities, and very low viscosity preparations can also be produced. So the viscosity (Brookfield rotational viscosity, measured in an LV viscometer) of the dispersions z. B. between 5 cp (spindle no. 2) and 10,000 cp (spindle no. 4), preferably between 50 cp (spindle no. 2) and 5,000 cp (spindle no. 4). The dispersions of the invention are also stable, i.e. that is, they can be stored for a long period of time without change, or if the dispersions separate into layers, they can be brought into the original, regularly dispersed form by simple stirring. Particularly noteworthy is the very good distributability in water or dilutability with water of the preparations according to the invention, in particular of the (c) -containing preparations, and indeed they can be diluted very quickly by simply adding the preparations to water or from water to the preparations with stirring or it is also possible to use the customary dilution apparatuses, as are customary in the art and also described in large numbers in the literature, for predilution with water. -12-

AT 397 215 B

Diluents that work with water jet pumps are particularly suitable; that is, the polymer dispersion is fed through one nozzle and the water through another nozzle into a &quot; chamber &quot; pumped that the water entrains the dispersion at high speed, after which the mixture in various ways, e.g. B. on baffle plates or walls or using high shear forces or by pumping in and out in &quot; resting tanks &quot;, in the water. A particularly valuable method for diluting the dispersions according to the invention with water is characterized in that the dispersion is introduced into a water flow through at least one nozzle such that the water flow flows around the nozzle, the volume flow of the water being higher than the volume flow of the dispersion and the speed of the water is so much higher than the speed of the dispersion that the dispersion is dragged along by the water flow in such a way that the adhesion and / or cohesion forces in the dispersion are at least partially overcome, but essentially not so high shear forces in the flow arise that the molecules in the dispersion are thereby crushed, the product-water mixture is then accelerated through a narrow pipe and then slowed down again in an expanded mixing zone, the acceleration and deceleration being carried out until the desired distribution of the product in water, and after the dispersion and water come into contact, the process is carried out without the use of filters or screens.

Due to the very rapid dilutability with water of the preparations according to the invention, many large-scale, continuously carried out processes in which cationic polymers are used can be carried out very efficiently and with an optimal metering rate. It is also particularly worth mentioning that the preparations according to the invention can have a very high concentration of cationic polymers. In addition, the biological eliminability of the preparations can also be mentioned. The preparations according to the invention are notable for their dilutability with water and dispersibility in water, and the invention comprises such preparations in any concentration, provided that they can still be diluted with water or the polymers are soluble or dispersible or dissolved or dispersed in water. In particular, both highly concentrated preparations are meant, in particular those which contain at least 10% by weight of cationic polymer, and also prediluted preparations, in particular those which contain at least 0.001% by weight, preferably at least 0.1% by weight, of cationic polymer.

The preparations according to the invention can be used in all fields of technology in which cationic water-soluble polymers are used, in particular they can be used as flocculants, and a further subject of the invention is the use of the preparations according to the invention as rocking agents, preferably as retention and drainage agents for paper , and as a flocculant for aqueous sludge, especially digested sludge and fresh sludge from municipal sewage treatment plants. The invention also relates to the process for the production of paper, which is characterized in that a preparation according to the invention is used as the retention and / or drainage agent.

A particularly homogeneous sheet formation can be observed in the production of paper using the preparations according to the invention.

The required concentration of the preparation for the respective application depends, of course, on the concentration of active substance (polymer) for the respective flocculation.

In the following examples, the parts are parts by weight and the percentages are by weight; the temperatures are given in degrees Celsius. Unless otherwise stated, the products used are commercially available products.

Example 1 43.5 parts of emulsifier (Βχ) are mixed with 800 parts of water, resulting in a very fine, opalescent emulsion. Now 8.2 parts of calcium chloride are added to form the calcium salt of (Βχ). A strong precipitation is immediately observed, which corresponds to the formation of the water-insoluble (oil-soluble) calcium sulfonate. 440 parts of White Spirit (Cj) are then added with stirring. A water-in-oil emulsion is formed, which is stabilized by adding 99.5 parts of emulsifier (Dj). This water-in-oil emulsion is then in the order given 353 parts of a 75% aqueous methacryloyloxyethyltrimethylammonium chloride solution, 454 parts of acrylamide, 1.4 parts of ethylenediaminetetraacetic acid, di-sodium salt, 0.7 part of iron (III) sulfate and 0 , 7 parts of tert-butyl hydroperoxide were added. The pH of the aqueous phase is approximately 3. Then the dispersion obtained is rendered inert with nitrogen and heated to 35 °. As soon as this temperature is reached, an air-free solution of 2.7 parts of sodium thiosulfate in 50 parts of water is started to be added dropwise. The addition takes place within 8 hours, the temperature being kept between 35 and 40 ° by cooling. After the addition of the sodium thiosulfate solution, the polymerization reaction is complete. A stable, fine, low-viscosity polymer-containing dispersion is obtained which has a viscosity of 1,000 cp (Brookfield, spindle 3.60 rpm). The product can be diluted very well with water: approx. 30 to 40 seconds after the addition -13-

AT 397 215 B for cold water the maximum viscosity has already been reached with a 1: 200 (= 0.5%) aqueous dilution. The viscosity of a freshly prepared 1: 100 diluted (= 1%) aqueous preparation is approx. 500 cp. (Brookfield, spindle 3.60 rpm).

Example 2 454 parts of acrylamide, 353 parts of a 75% aqueous methacryloyloxyethyltrimethylammonium chloride solution, 1.4 parts of ethylenediaminetetraacetic acid, di-sodium salt, 0.7 part of iron (III) sulfate, and 9.8 parts of calcium chloride are added to 600 parts of water in the order given with stirring. The solution obtained is then mixed with a solution of 52 parts of emulsifier (B j) and 80 parts of emulsifier (Dj) in 600 parts of White Spirit (Cj). A water-in-oil emulsion with a pH value (aqueous Phase) of 3, which is then injected with nitrogen. Then, to initiate the polymerization reaction, first 0.7 parts of terL-butyl hydroperoxide and then an air-free solution of 1.1 parts of sodium thiosulfate in 12 parts of water are added.A strongly exothermic reaction occurs immediately, the temperature, despite being slightly cooled, from room temperature to 90 ° increases A thin, polymer-containing dispersion which can be easily diluted with water is obtained.

Example 3 24 parts of emulsifier (Bj) are mixed with 480 parts of water, giving a very fine, opalescent emulsion. 564 parts of a 75% strength aqueous methacryloyloxyethyltrimethylammonium chloride solution are then added to form the corresponding methacryloyloxyethyltrimethylammonium petroleum sulfonate. Then, in the order given, with stirring , 408.3 parts of acrylamide, 1.43 parts of ethylenediaminetetraacetic acid, di-sodium salt, 0.77 parts of iron (III) sulfate, 480 parts of White Spirit (Cj), 30 parts of emulsifier (Dj), 30 parts of emulsifier (D2), 4.8 parts of calcium chloride and 0.6 part of terL butyl hydroperoxide were added. The dispersion obtained is then rendered inert with nitrogen and heated to 30 °. Once this temperature has been reached, an air-free solution of 2.97 parts of sodium thiosulfate in 42 parts of water is started to be added dropwise. The addition takes place within 8 hours, the temperature rising to 50 °. A fine polymer-containing dispersion is obtained which can be readily thinned with water.

Example 4 500 parts of the preparation obtained according to Example 1 are mixed with 10 parts of White Spirit (Cj) and 10 parts of emulsifier (0¾) with stirring. The mixture is then evacuated to 26 mbar and the temperature is raised from room temperature to 40 °, with about 200 parts of water using a water separator be distilled off regularly. The result is a fine, stable polymer-containing dispersion which can be diluted well with water

Example 5

The procedure is as described in Example 1, and 10% (based on the weight of the preparation obtained according to Example 1) of the 20% preparation according to Example 3.1 from FR-PS 1583 363 are added to the preparation obtained with stirring, whereby a stable W / O emulsion.

Example 6

Part 1: Dispersion ΠΊ 454 parts of acrylamide, 353 parts of a 75% aqueous solution of methacryloyloxyethyltrimethylammonium chloride and 800 parts of water are loaded into a sulfonation flask and stirred. After the acrylamide has dissolved, 1.43 parts of ethylenediaminetetraacetic acid, disodium salt and 0.72 parts of iron (III) sulfate are added to the reaction solution and the pH is adjusted to 3 by adding about 0.1 part of 30% sodium hydroxide solution. A solution of 143 parts of emulsifier (D j) in 440 parts of White Spirit (C2) is then allowed to flow into the monomer solution with vigorous stirring. A milk-like water-in-oil emulsion is formed, which is then evacuated 5 times to a pressure of 26 mbar and relieved in each case with nitrogen.

A strong stream of nitrogen is then passed through the air-free emulsion at high stirring speed. 0.67 part of terL-butyl hydroperoxide is then added to the cold reaction mixture and the mixture is heated to 35 °. As soon as this temperature is sufficient, 50 parts of a solution of 2 parts of sodium thiosulfate in 50 parts of water are added dropwise to the monomer emulsion within 5 hours. The exothermic polymerization reaction commences during the addition of thiosulfate, the temperature being kept at 36 to 38 ° by gentle cooling. The mixture is then left to react for a further 2 hours at 35 ° and then cooled to room temperature, the nitrogen supply is switched off and discharged. -14-

AT 397 215 B

Part 2: 200 parts of the dispersion (1) prepared in accordance with Part 1 are mixed with 20 parts of White Spirit (C2) and 20 parts of a »30% mineral oil solution of petroleum sulfonate (Bj) in the form of the calcium salt. A viscous product is obtained which, however, despite the high viscosity, can be quickly diluted with water when added to water (e.g. 4 parts 5 product to 396 parts water).

Part 3: Production of (b ^

The petroleum sulfonate (Bj) in the form of the calcium salt is prepared by treating a 20% strength aqueous emulsion of (B j) (sodium salt) with an excess of CaCl2, filtering off the precipitated (B j) calcium salt, washing 10 with water and under Vacuum dries at 60 to 70 °.

Example 7 200 parts of dispersion (1) according to Example 6 (part 1) are mixed with 25 parts of a solution of 10 parts of a paraffin sulfonate (B3). The mixture obtained can be diluted very well with water. The calcium salt 15 of the surfactant (B3) is prepared analogously to that described in Example 6, Part 3, the appropriate amount (B3) being used instead of (B j).

Example 8 200 parts of the dispersion (1) according to Example 6 (Part 1) are mixed with 30 parts of a solution of 14.3% 20 petroleum sulfonate Na salt (B2), 57.1% mineral oil (C3) and 28.6% of a 50 % solution of triisobutyl phosphate (Fj) in isobutanol is added. A viscous product is obtained which can be easily diluted when added to water.

EXAMPLE 9 25 2210 parts of the polymer-containing emulsion prepared according to Example 1 are, after the addition of 330 parts of mineral oil (C3) and 330 parts of petrolatum (C4), evacuated to 26 mbar with stirring and heated to 40 ° in the course of about 6 hours, 860 Parts of water are regularly distilled off using a water separator. Together with water, a little oil distills, which collects in the water separator on the surface of the water and is regularly returned to the reaction vessel. A very fine, stable, slightly viscous dispersion is obtained which can be diluted with water approximately as well as the product according to Example 1.

Example 10

A nitrogen-dispersed dispersion consisting of 960 parts of water, 816.6 parts of acrylamide, 1128 parts of a 75% strength aqueous methacryloyloxyethyltrimethylammonium chloride solution, 2.9 parts of 35 ethylenediaminetetraacetic acid, di-sodium salt, 1.5 parts of iron (III) sulfate, 9.1 Parts of calcium chloride, 48 parts of emulsifier (Bj), 60 parts of emulsifier (Dj), 60 parts of emulsifier (D2) and 960 parts of White Spirit (Cj), which were adjusted to pH 3 with a little sulfuric acid, are first used to initiate the polymerization reaction 1, 2 parts of tert-butyl hydroperoxide were added. Then the dropwise addition of an air-free solution of 6.5 parts of sodium thiosulfate in 20 parts of water is started. The addition takes place within 8 hours, the temperature 40 rising to about 48 ° despite cooling. After the thiosulfate has been added, 165.7 parts of mineral oil (C3) and 27.7 parts of emulsifier (D3) are added to the polymer-containing emulsion. Then distilled under vacuum (20 to 26 mbar) and at an internal temperature of at most 50 ° using a water separator from about 1186 g of water. A very fine, thin, liquid dispersion is obtained which, after the water has been distilled off, is mixed with 157.5 parts of olive oil (C5) and 157.5 parts of 2-ethylhexanol (F2). The olive oil and 45 2-ethylhexanol-containing dispersion can be instantly diluted in water.

Example 11

The procedure is exactly the same as in Example 10, but the 2-ethylhexanol (¾) is replaced by triisobutyl phosphate (Fj). 50

Example 12

The procedure is exactly the same as in Example 10, but the 2-ethylhexanol (¾) is replaced by tributoxyethyl phosphate (F3) 55 Example 13

The procedure is exactly the same as in Example 10, but the 2-ethylhexanol (F2) is replaced with 2,4,7,9-tetramethyl-5-decyn-4,7-diol (F4). -15-

AT 397 215 B

Example 14 43.5 parts of emulsifier (Bj) are mixed with 834 parts of water, a very fine, opalescent emulsion being formed. Now 8.2 parts of calcium chloride are added to form the calcium salt of (Bj). 557 parts of acrylamide, 216 parts of a 75% strength aqueous methacryloyloxyethyltrimethylammonium chloride solution, 1.4 parts of ethylenediaminetetraacetic acid, di-sodium salt and 0.7 part of iron (in) sulfate are then added with stirring, a cloudy solution being formed. 400 parts of isoparaffinic solvent (Cg), 40 parts of mineral oil (C3), 100 parts of emulsifier (Dj) and 13 parts of emulsifier (B ^) are then added. A water-in-oil emulsion is formed, which is inertized with nitrogen. Then 0.7 part of tert-butyl hydroperoxide and then 6 parts of a solution of 2.7 parts of sodium thiosulfate in 50 parts of water are added dropwise to initiate the polymerization reaction. An exothermic reaction occurs, the temperature rising to 85® despite cooling.

Example 15

The procedure is analogous to that described in Example 14, except that 709 parts of water are used instead of 834 parts, 1833 parts of acrylamide instead of 557 parts, 714 parts of 75% strength methacryloyloxyethyltrimethylammonium chloride solution instead of 216 parts. The temperature rises to about 43 ° under adiabatic conditions. After the polymerization, 33 parts of Pluronic L101 (Fg) and 165 parts of fatty acid methyl ester mixture (C7) are added.

Example 16

The procedure is analogous to that described in Example 14, but 160 parts of mineral oil (Cg) are used instead of 40 parts. The temperature is kept between 35 and 40 °.

Example 17

43.5 parts of emulsifier (B j) are mixed with 800 parts of water, producing a fine, opalescent emulsion. Then, in the order given, 8.2 parts calcium chloride, 363 parts acrylamide, 124 parts diallylamine, 353 parts 75% methacryloyloxyethyltrimethylammonium chloride solution, 131 parts hydrochloric acid (34%) to adjust the pH to 3.1.4 parts Ethylenediaminetetraacetic acid, disodium salt and 0.7 part of iron (III) sulfate were added. A homogeneous monomer solution is formed, to which 400 parts of white spirit (C j), 40 parts of mineral oil (C3) and 100 parts of emulsifier (Dj) are then added. A fine emulsion is formed, which is rendered inert with nitrogen. Then 0.7 part of tert-butyl hydroperoxide and then 160 parts of a solution of 2.7 parts of sodium thiosulfate in 50 parts of water are added dropwise to start the polymerization reaction. An exothermic reaction occurs and the temperature rises to 65 ° under adiabatic conditions

Example 18

The procedure is analogous to that described in Example 2, 29 parts being used instead of 52 parts of emulsifier (B]) and 49 parts of emulsifier (D3) and 65 parts of emulsifier (D4) instead of γοη 80 parts of emulsifier (D1).

Example 19 43.5 parts of emulsifier (B j) are mixed with 800 parts of water, a fine, opalescent emulsion being formed. Now 8.2 parts of calcium chloride and then 454 parts of acrylamide, 353 parts of a 75% strength aqueous methacryloyloxyethyltrimethylammonium chloride solution, 1.4 parts of ethylenediaminetetraacetic acid di-sodium salt and 0.7 part of iron (III) sulfate are added. The solution obtained is then mixed with 400 parts of White Spirit (Cj), 40 parts of mineral oil (C3), 100 parts of emulsifier (Dj) and 54 parts of emulsifier (B2). A water-in-oil emulsion is formed, which is inertized with nitrogen. Then 0.7 part of tert-butyl hydroperoxide and then 45 parts of a solution of 2.7 parts of sodium thiosulfate in 50 parts of water are added dropwise to initiate the polymerization reaction. A strongly exothermic reaction occurs, the temperature rising to 90 ° within about 90 minutes.

Example 20 43.5 parts of emulsifier (B j) are mixed with 600 parts of water. 8.2 parts of calcium chloride, 454 parts of acrylamide, 1.4 parts of ethylenediaminetetraacetic acid, di-sodium salt, 0.7 part of iron (III) sulfate, 400 parts of white spirit (C), 40 parts of mineral oil ^), 10 parts of emulsifier (Di ) and 13 parts emulsifier (B2) added. A water-in-oil emulsion is formed, which is then rendered inert with nitrogen and mixed with 0.7 part of tert-butyl hydroperoxide and 1 part of a solution of 2.7 parts of sodium thiosulfate in 50 parts of water. The exothermic polymerization reaction occurs immediately, the temperature being kept at about 60 °. Shortly before the exothermic reaction subsided, one of the air efficiencies -16-

AT 397 215 B solution of 265 parts of methacryloylethyltrimethylammonium chloride in 288 parts of water, the temperature rising again and being kept at 55 to 60 ° by cooling. After the exothermic polymerization reaction, the mixture is stirred for a further 1 hour at 55 ° and cooled to room temperature (20 °)

Example 21

The procedure is analogous to that described in Example 15, but using 11 parts of emulsifier (Bj) instead of 43.5 parts, 25 parts of emulsifier (Dj) instead of 100 parts, 3.25 parts of emulsifier (B2) instead of 13 parts and after the polymerization (F5) and (C7) are not added.

Example 22

The procedure is analogous to that described in Example 16, but using 21.75 parts of emulsifier (Bj) instead of 43.5 parts, 50 parts of emulsifier (Dj) instead of 100 parts and 6.5 parts of emulsifier (Bj) instead of 13 parts.

Emulsifiers used Emulsifier (B ^ V 62% solution of a petroleum sulfonate (monosulfonate) in the form of the sodium salt with a molecular weight of 440 to 470 in mineral oil.

Emulsifier (Bo): 60% solution of a petroleum sulfonate (monosulfonate) in the form of the sodium salt with a molecular weight of 480 in mineral oil.

Emulsifier (B31:

Secondary n-alkanesulfonates in the form of the sodium salts produced by sulfoxidation of paraffins, in which the alkane radical has the following average composition: C13 - Cj5 = 58%

Ci6-Cn = 39% &gt; Cj7 &lt; 3% &lt; C13 <1%

Emulsifier (D ^:

Cl2H25- (° CH2CH2) 2- ° H HLB = 6.5

Emulsifier (Pol: C18H35- (OCH2CH2) 3-OH HLB = 6.5

Emulsifier ('Dg'):

Sorbitan monooleate HLB = 4.0

Emulsifier CD /] !:

Mixture of C17H33CO (OCH2CH2) 6) 5-0-CO-C17H33 and C17H33CO (OCH2CH2) öi50Him molar ratio 1: 1 average HLB = 7.0

Oils used:

White Spirit aromatics-free terpenaline, boiling range 193-247 °, average molecular weight 173.

White Spirit CCol: low aromatic terpenaline, boiling range 190-250 °, average molecular weight 180, aromatic content 0.5%. Mineral oil (C31: partially unsaturated mineral oil with the following specifications:

Density 0.85 - 0.95 aniline point 70 - 80 °

Iodine number 20 - 30. -17-

AT 397 215 B

Petrolatum fC /] l:

Petrolatum with solidification point = 50 - 85 ° and cone penetration at 25 ° = 160-180

Olive oil (C $):

Isooaraffin (CGI:

Isonaraffinic oil with:

Boiling range 210 - 260 °

Aniline point 88 °

Isoparaffin content 80%

Density 0.78

Fatty acid methyl ester mixture (Cj):

Methyl esters of Cj2 to C20 fatty acids with the following specifications:

Density 0.87-0.90 acid number 1.12 saponification number 190-200 iodine number 100-110 hydroxyl number 40-60

Mineral oil (Cg);

Hydrocarbon mixture with the following specifications:

Density 0.85-0.95 aniline point 95 °

Viscosity (20 °) 30 cp

Solvents used (fl: (Fj) triisobutyl phosphate (50% solution in isobutanol) (F2) 2-ethylhexanol (F3) tributoxyethyl phosphate (F4) 2,4,7,9-tetramethyl-5-decyn-4,7-diol ( F5) Pluronic L101: ethylene oxide-propylene oxide copolymer with a molecular weight of 3610 and 10% by weight of ethylene oxide units.

Dilution Heisniel I

A mixer is used in which a tearing chamber and 5 mixing chambers are arranged horizontally and represent a cylinder with a horizontal axis. The inner diameter of the individual chambers is 110 mm and the inner volume of each chamber is 2.5.10 '^ nA Der The inner diameter of the pipe for the water supply of the connecting hoses between the tearing chamber and the mixing chamber and between the mixing chambers and the line for the removal of the diluted product are the same. The connecting hoses between the chambers as well as their nozzles have an inner diameter of 15 mm; the length of the hoses is 40 cm each. 10 l / h of the preparation according to Example 1 (polymer emulsion), in pulses, at a frequency of 50 sec &quot; into the tearing chamber of the mixer through a polymer nozzle provided with a check valve and an opening of 2 mm in diameter. ^ and pumped through a water nozzle with an opening of 15 mm diameter 2000 (1 / h) water. The speed of the water at the nozzle opening is 3.2 m / s (= Re 47000) and it flows around the entire polymer nozzle. The diluted product emerging from the mixer is a ready-to-use aqueous solution of the polymer and is ready for use in papermaking.

Dilution example Π

The procedure is as described in Example 1, but using a mixer in which the polymer nozzle has 6 openings each 1 mm in diameter, and 51 / h of polymer emulsion according to Example 1 are pumped into the mixer. The diluted product emerging from the mixer is a ready-to-use aqueous solution of the polymer and is ready for use in papermaking.

Appiikationsheisniei A

A 2% aqueous paper pulp of the following solid composition is used:

AT 397 215 B 100 parts bleached sulfite pulp 20 parts kaolin 3 parts resin glue 2 parts aluminum sulfate 5

Before the sheet is formed on the Rapid-Köthen sheet former, 250 ml of test substance with 5 resp. 10.15 and 20 ml of a 0.0125% aqueous dilution of the product according to Example 1 and 750 ml of dilution water are mixed. After a stirring time of 5 seconds at 250 revolutions / minute, the substance / water mixture is poured into the filling chamber of the sheet former (system Rapid-Koethen) transferred, 31 water being placed in the filling chamber 31. After a holding time of 20 seconds, the sheet is formed by actuating the suction valve. After the test sheets have been dried and conditioned, they are incinerated. The ash content is related to the filler used and expressed in% retention. The result is summarized in the following table; the values given for% ash and% retention are mean values of two determinations. 15

Amount added in ml 0.0125% solution Flocculant concentration * in% (based on dry paper stock)% ash% retention 5 0.0125 13.31 79.9 10 0.025 14.34 86.0 15 0.0375 14.66 88 .0 20 0.05 14.73 88.4 zero value • 8.51 51.1 30 * (polymer emulsion)

APPLICATION EXAMPLES B 200 parts of a digested sludge suspension with 5% dry matter content are initially mixed with w parts of a 35.23% aqueous dilution of the preparation prepared according to Example 1 and then for 10 seconds using a &quot; Triton &quot; Stirrer stirred at a speed of 1000 revolutions / minute. Then the sludge suspension is immediately filtered on a fabric filter and the mean volume of the filtrate is determined after 30, 60, 90, 120 and 180 seconds. w Average volume 0 1.5 parts by volume 13 15.3 15 40.4 17 49.1 19 81.9

The products of Examples 2-22 can be used in a manner analogous to that described in Application Examples A and B. -19- 55

Claims (11)

AT 397 215 B PATENT CLAIMS 1. Water-dilutable, polymer, surfactant and oil-containing preparations, characterized in that they (a) a hydrophilic, cationic polymer, (b) at least one sulfonated hydrocarbon as anionic surfactant, (c) at least one oil immiscible with water, in which the polymer is not soluble, but is finely divided therein, (d) a lipophilic or oil-soluble, nonionic surfactant and / or (e) water and optionally (f) an oil-miscible, in Water-insoluble and non-self-dispersible, polar solvent, which alone has no emulsifier properties, but contains a reduced water / oil interfacial tension, the molar proportion of anionic surfactant (b) being no greater than the molar proportion of cationic monomer units of the polymer (a) and where appropriate the cation of the polymer and the anion of the anionic surfactant are combined to form the salt . 2. Preparations according to claim 1, characterized in that (c) is a mixture of oils (q) and (c2) which is chosen so that the O / W EHLB value of (q) is greater than that E / W-EHLB value of the mixture (q) + (cq). 3. Preparations according to claims 1 and 2, characterized in that they contain at least 10% by weight of component (a). 4. Preparations according to claims 1 to 3, characterized in that they contain 0.5 to 30 parts of component (b) and 30 to 400 parts of component (c) per 100 parts of component (a). 5. Preparations according to claims 1 to 3, characterized in that they contain such an amount of water that the polymer is finely dispersed together with the water in the oil. 6. A process for the preparation of preparations according to claims 1 to 5, characterized in that the anionic surfactant (b) is combined before, during and / or after the polymerization with the polymer (a) or with the corresponding monomers. 7. Process for the preparation of preparations according to Claim 1, characterized in that component (b) is reacted with the polymer (a) or the corresponding monomers before, during or after the emulsion polymerization in the presence of (e) and optionally (d), at least some of the surfactants (b) and / or (d) being present during the emulsion polymerization, and, if appropriate after distilling off (e) and / or (c), optionally with further components (a), (b), ( c), (d), (e) and / or (f). 8. A process for the preparation of preparations according to claims 1 to 7, characterized in that a) an oily dispersion comprising a hydrophilic, cationic polymer (a), water (e) and a lipophilic or oil-soluble, non-ionic surfactant (d) contains a lipophilic or oil-soluble, practically water-insoluble, anionic surfactant (b), the oil in the oily dispersion being a water-immiscible hydrocarbon oil (C3) in which the polymer (a) is fine with the water is distributed, and optionally component (f) is added together with (b) and / or (b) is added as a solution in the oil (C3); or β) for the preparation of preparations which, as (a) contain cationic polymers (aj) of vinyl-like monomers, polymerize the monomers required for forming the cationic polymers (aj) in the presence of anionic surfactants (b) in a W / O emulsion and if desired, water and / or oil are distilled off and, if appropriate, further additives (a), (b), (c), (d), (e) and / or (f) are added, or γ) according to variant β), with at least one Part of the cationic monomers is in the form of a W / O emulsion of monomer salts, in which the monomer salts are those in which the cation is that of a vinyl-like -20-AT 397 215 B cationic monomer and the anion is that of an anionic surfactant (b), or δ ) for the preparation of preparations which, as (a) contain copolymers (aj) of cationic and nonionic vinyl-like monomers, the nonionic monomers or a part thereof by the inverse emulsion polymerization process in the presence of n (c), (d) and (e) prepolymerized and, after addition of the cationic monomers and optionally the remaining part of the non-ionic monomers, polymerized to the end in the presence of (b), with (b) before, after or together with the cationic monomers and / or in the form of monomer salts, in which the surfactant anion is the counter ion of the monomer cation. 9. W / O emulsions containing vinyl-like monomer salts, in which the cation is that of a vinyl-like cationic monomer and the anion is that of an anionic surfactant (b), optionally in addition to emulsifier (d), the oil being an oil (c) which is like is defined in claim 1 or 2 and (b) and (d) are as defined in claim 1. 10. Use of the preparations according to claims 1 to 4 as a flocculant. 11. Use according to claim 10 for the production of paper and / or for wastewater treatment.