SE458526B - POLYMERIZED AND DENSID PREPARATIONS, THEIR PREPARATION AND APPLICATION AS A FLEXIBLE AGENT - Google Patents

Description

The polymers a) are preferably at least partially a1) cationic homo- and / or copolymers of vinyl-like cationic and possibly non-ionic monomers, wherein with advantage the polymers a) mainly consist of a1); anaeien a1) 1 a) preferably constitutes at least 70% by weight, in particular at least 90% by weight; in particular, a) preferably consists exclusively of a1).

Preferred monomers for the preparation of a1) are vinyl-like, water-soluble monomers, preferably those of the acrylic and methacrylic acid ester series, of the acrylic and methacrylic acid amide series, of the vinylpyridine series, of the diallylamine series, of the N-vinylpyrrolidone series, as well as such av avers.

Pöredragna representatives of the above classes of mono- Mere from cationic-type is; akrylsyradialkylaminoalkylestrar, akrylsyratrialkylammoniumalkylestrar, metakrylsyradialkylamine- esters, metakrylsyratrialkylammoniumalkylestrar, dialkylaminohydroxialkylestrar acrylic acid, acrylic acid trialkylammoniumhydroxialkylestrar, dialkylaminohydroxialkylestrar methacrylic acid, methacrylic acid trialkylammoniumhydroxialkylestrar, 2- and 4- vinyl pyridine and the corresponding N-alkylpyridiniumderivat, N-alkyl diallyl amine and the corresponding N-dialkyldiallylammoniumderivat, acrylic dia lkylaminoalkylaxuider Q akrylsyratr ialkylanunon iuma lkylamíder, meth acrylic acid dialkylaminoalkylæmdénfmetakrylsyratrialkylammonium- ancestry ducks, akryisyraaiaikyisuifoniumaikyiesrrar and metakryisyra- dialkylsulfoniumalkylestrar; Alkylene bridge link (namely between N and O, between 0 and S and between N and N) advantageously contains 2 to 4, preferably 2 to 3 carbon atoms; terminal alkyl groups (especially substituents on basic nitrogen or sulfur) advantageously contain 1 to 4, preferably 1 to 2 carbon atoms and may optionally be substituted by phenyl: are they substituted by phenyl. mainly concerns benzyl; preferably, however, the alkyl residues are unsubstituted.

Among the cationic monomers cited, those having the following formulas are particularly preferred: fR2 \ cu2 = c-co-o-ca -ca -N-2 2 121 Ra (I) \\.

R 1, / 2A (:) ca = c-co-o-en -ca -N - R 2 2 2 3 \\\ R R1 4 R ca = c-co-o-ca -cnou-ca -N '/ I 2 2 | 2 2 \\ R R1 3 cnz = c-co-o-CH2-cnoa-cnz-N (E) .___ R 1 R ca æ-co-NH- (cn pN / 2 2 I 2 n \ R1 Rs R 2 '_ °' 2 n __ "3 ca -c co Nu (ca) Rz 1: 1 \ R _ 4 ca = cH-ca 2 2 \ N-R2 cn2 = cn-caz ca = c fl- ca R 2 2 2 \ (+) Nf: _ AC3 _ ff _ca2-ca-caz R4 1 4558 AC) 5226 (II) r (III).

(IV).

(V) I - ri (VI), (VII).

(VIII) f 10 15 20 25 4 cH2 = cH cH2 = c fl cH2 = cH \\ L§ = N 1 l, I / | AB R 4 (IX), (X), (XI), (XII) wherein R 1 represents hydrogen or methyl, R 2 is methyl or ethyl, R 3 is methyl or ethyl, R 4 is hydrogen, methyl or ethyl, A (:) is a counterion to the ammonium group , and n 2 or 3.

The symbol Ac1) generally denotes an arbitrary anion, as is usual with ammonium compounds, advantageously a halide ion (in particular chloride, bromide or iodide) or an R 50 - 4 4 anion. The symbols R2 and R3 preferably denote míššl. In a particular embodiment of the invention, however, A also denotes (A1), i.e. the anion of an anionic, preferably lipophilic, preferably oil-soluble surfactant as defined in more detail below.

Of the cationic monomer units, acrylic and methacrylic acid derivatives are generally preferred, preferably optionally quaternized acrylic acid or methacrylic acid dialkylaminoalkyl esters and dialkylaminoalkylamides: resp. among the listed monomer compounds, those of formulas (I) to (VI), especially those of formulas (I), (II), (V) and (VI) are preferred. Particularly preferred cationic monomers are those of formulas (I) and (II).

Preferred representatives of the stated classes of non-ionic monomers are those of the following formulas: CH2 =? CONH2 R1 (XIII), safta-HQ (XIV), äncca-o-Rs (XV) ) and cnfe-co-Nn-c (C113) 2-c112-co-cH3 (xvI), R1 wherein R5 represents methyl or ethyl and R1 has the meaning given above.

Among the nonionic monomers listed, those of formula (XIII) are particularly preferred, i.e. methacrylamide and acrylamide.

Preferred polymers a1) are copolymers of cationic monomers of formula (I) and / or (II) and non-ionic monomers of formula (XIII).

The polymer a), in particular a1) intended for insertion according to the invention, are cationic, i.e. at least some of the corresponding monomers are cationic monomers and any others are non-ionic; advantageously the proportion of cationic monomer units is 5-100 mol%, preferably 10-80 mol%, in particular 10-40 mol%. To achieve certain effects or to set certain cation contents, it can also be an advantage to use two polymers with different cation contents, ie. of a weaker cationic and a stronger cationic polymer, and if desired mix them together; suitable weaker cationic polymers are those whose proportion of cationic monomer units advantageously is S to Z0 mo1%, suitable stronger cationic polymers are those which proportion of cationic monomer units advantageously is 20 to 80%, preferably 30 to 60 mol%.

The average molecular weight (weight average) of the polymer phosphate can be arbitrarily high, e.g. up to 20,000,000, advantageously they have an average molecular weight of 100,000, 1,000,000.

As component b), i.e. as the anionic surfactant is preferably 2,500,000, especially preferred à generally arbitrary, customary surfactants which contain at least one lipophilic hydrocarbon residue and at least one hydrophilic anionic group, such as the e.g. described in the "Surfactant Science Series" (M. Dekker 10 15 20 25 30 35 458 526 6 Inc., New York and Basel), vol. 7: "Anionic Surfactants" (edited by Warner M, Linfield, 1976) - parts 1 and 2 -; the lipophilic residue is preferably araliphatic or aliphatic and advantageously contains at least 9 carbon atoms, preferably 12-36 carbon atoms; the anionic group may be any conventional acid group, which may be present in salt form, preferably carboxylate, phosphate, phosphonate, sulphate and sulphonate, of which carboxylate, phosphate, sulphate and sulphonate are preferred, but above all the sulphonate group; optionally, polyalkylene glycol ether groups may also be present in the molecule of the anionic surfactant, however, the surfactants preferably do not contain any polyalkylene glycol ether groups. Particularly noteworthy classes of anionic surfactants are the following: sulfurized fatty acid mono-, di- and triglycerides (in particular sulfurized, natural fats or oils or sulfurized monoglycerides), sulfurized fatty alcohols and sulfurized fatty acid alkanolamides; sulfonated hydrocarbons, preferably alkyl sulfonates, olefin sulfonates and alkylaryl sulfonates, especially petroleum sulfonates; sulphonated aliphatic carboxylic acids and carboxylic acid esters, in particular 65-sulphomonocarboxylic acids and p (-sulphomonocarboxylic acid esters and sulphosuccinic acid alkyl esters; phosphoric acid alkyl partial esters; aliphatic carboxylic acids (soaps) and carboxymethylating fatty alcohols;

Among the listed anionic surfactants, sulfonates are particularly preferred, especially petroleum sulfonates.

The anionic surfactants are advantageously present at least in part e.g. in the form of salt, whereby for salt formation there are arbitrary, common cations, e.g. alkali metal cations (lithium, sodium, potassium), ammonium cations [unsubstituted ammonium as well as substituted ammonium, e.g. mono-, di- and tri- (C 1-8 alkyl) ammonium and mono-, di- and tri- (C 2-3 alkanol) ammonium, in particular mono-, di- and triethylammonium, mono-, di- and triisopropanolammonium and mono-, di- and triethanolammonium], alkaline earth metal cations (magnesium, calcium, strontium and barium) and additional polyvalent cations. in particular Zn2 + I Al3 +, Zr4 +. As preferred, anionic surfactants are in the form of corresponding salts of polyvalent inorganic cations, with calcium being especially preferred.

The anionic surfactants may have a more or less pronounced water solubility resp. dispersibility or may be practically insoluble in water (ie they give in the concentrations used no real solution in water, but may nevertheless be dispersible in water and / or preferably dispersible or soluble in oil), which essentially depends on the choice of lipophilic residue and the choice of cation. Preferred anionic surfactants are lipophilic, preferably those which in the form of Na salt are oil soluble, in particular those which are in the form of salts with such cations (preferably polyvalent inorganic cations), that the water does not give any real solutions and with water and with corresponding oils, in particular as defined below under c), gives W / O emulsions, i.e. they have a W / 0 emulsifier character, resp. they are W / O emulsifiers.

The anionic surfactants listed above are generally known or can be prepared in a manner known per se. Amine salts and salts of polyvalent inorganic cations of anionic surfactants are prepared e.g. advantageously in situ, by advantageously reacting alkali metal salts of these surfactants with water-soluble salts of the corresponding amines, resp. polyvalent inorganic cations. Suitable water-soluble salts are essentially salts of strong inorganic acids (each time after cation with the advantage of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid) and simpler organic carboxylic acids (C1-4-carboxylic acids, preferably formic acid and acetic acid). amine salts, sulphates, chlorides and acetates are preferred and of salts polyvalent inorganic cations, formates and above all chlorides are preferred.

Particularly preferred is the insertion of calcium chloride.

If the polymers contain cationic monomer units, the counterion of which is a surfactant amine, then its proportion in the polymer molecule advantageously constitutes on average not more than 15 mol%, preferably not more than 10 mol%.

In general, the polymers in the compositions of the invention contain cationic monomer units and optionally non-ionic monomer units, some of the cationic monomer units containing the anion of the anionic surfactant as a counterion to the cation. Schematically, the polymers can be illustrated as 458 526, in those containing the following recurring monomer units: ... Q- I (05) (Katæ fl l fi ê) _ Q _ I (ß) (MJÜHAZQ) and optionally -G - (f fi wherein (GL) and LA) are cationic monomer units, i.e. recurring cationic moieties, derived from cationic monomers, (3 ') i.e. -G- are non-ionic monomer units, i.e. recurring, non-ionic units. derived from non-ionic monomers, Q the portion of a monomer moiety included in the basic structure and Kat denoting the cationic moiety attached thereto, and (A1) a surfactant and (A2) a non-surfactant anion.

Preferred monomer units (K) and (ß) each correspond to the formulas F: -cn-c- 2 (ag) 'Q e: (Kat) (A1) R | 1 -CH2 C - (Meadow x (A29) wherein ( aa) and 041) respectively. (Cat (:)) are preferably those residues which correspond to derivatives of formulas (II), (IV), (VI), (VIII), (XI) and (XII). A wa 1 is preferably an anion of one of the above surfactants, advantageously one of a lipophilic surfactant (as defined above), in particular one of the above sulfonates. A2 preferably represents one of the above-mentioned non-surfactant anions, such as one which, for example, is formed by quaternization and / or protonation, preferably halide or R 0 -SO 4 3 °. In particular, (04) resp. G11) for 10 15 20 25 30 35 "9 458 526 f1 -cuz - c - / nz co-o-cnz-cuz-N XRB (Aa1Q) (æz) R4 or R | 1 -cu - c - 2 RI 2 co-NH- (crx2) -¿-N R4 wherein Aa1 (:} is an anion of a petroleum sulfonate, in particular of a lipophilic petroleum sulfonate.

Preferred monomer units (ß) resp. (ß1) corresponds to the formulas R CH '1 R2. Y / E) co-o-cnz-cuz-N - R 3 (Aag) (ß 2) R 4 and * r R -CH 2 - É - + 2 0 "'NH- RB, R 4 wherein Aazcj represents chloride or R40 ~ 5O3C3.

Preferred monomer units (Y) are those corresponding to derivatives of monomers of the above formulas (XIII) to (XVI), preferably those of the formula, 1 -cnz - ç - (~ f1).

CO-NH2 in particular of the formula -cnz- (Izn - (yz).

CO-NH 2 10 15 20 25 30 35 458 526 i w Preferred polymers are those which contain the units (then), 081) and (animal), respectively. consists thereof, in particular those which contain the units üxz), 062) and (fä) resp. consists of.

Advantageously, the compositions further contain: c) a water-immiscible oil, in which it is insoluble, but is finely divided therein.

Particularly in this case, it is an advantage, the anionic surfactant b) the polymer that it b ') is a lipophilic, preferably oil-soluble anionic surfactant.

Component c) can be a uniform oil as well as a mixture of different oils. In general, arbitrary oils used for the preparation of water-soluble polymers containing emulsions and / or dispersions, and more particularly both natural and synthetic oils, are suitable. As natural oils, both oils from the processing of rock oil and also vegetable and animal oils (essentially triglycerides) are in question; as synthetic oils, synthetic hydrocarbons as well as modified paraffins (hydrocarbons) and fatty acid esters (preferably triglycerides and monoesters) are involved.

Particularly preferred categories of oils are the following: Hydrocarbons X-hydrocarbons from rock oil processing, preferably special gasoline, distilled from crude gasoline (boiling range 65-140 ° C) (disaromatized, including aromatic types) white spirits, test gasoline and white spirit gasoline (boiling range 100-131 ° C) .föraträaaavis 140-zoo ° c), 1 ayaaarnac =. aroma-free types of boiling range 100-270 ° C, preferably 140-z 50 ° C. fractions with an aromatic content: between 12 and 19% "1eo-21o ° c". fractions with an aromatic content of 24 and 45% "140-31o ° c. fractions with an aromatic content of ao-eos "1so-2so ° c. pure aromatic white spiral" 16o-31o ° c 10 15 20 25 30 35 1.1.3 1.1.4 1.1.5 1.2 1I3 which are 458 526 Aromatic-free hydrocarbons with isoparaffinic structure (xoklntervail 11o-zso ° c) Paraffin oils (= mineral oils) e.g. diesel oils, spindle oils, engine oils, cylinder oils, lubricating oils and petroleum oils Petrolatum (petrolate) synthesis hydrocarbons, preferably those of Fischer-Tropsch synthesis or high pressure hydrocarbon, in particular: 11 - synthetic gasoline boiling range 65-170 ° C - xogasin 1 Optionally alkyl substituted benzenes, preferably benzene, xylene, toluene, methylethyl and trimethylbenzenes, dimethylethyl and tetramethylene benzenes, optionally alkyl substituted benzenes, preferably benzene, xylene, toluene, methyl ethyl and trimethylbenzenes, dimethylethyl and tetramethylene benzenes. alkylbenzenes (C 6 -C 12 alkylbenzenes).

Natural vegetable or aminal triglycerides, in particular olive oil, peanut oil, cottonseed oil, coconut oil, beet oil, sunflower oil, corn germ oil, castor oil and clove oil.

Fatty acid monoesters, preferably C 1-4 alkyl esters of C 12-24, preferably C 14-24 fatty acids, in particular: methyl, butyl and isopropyl esters of stearic acid, oleic acid, palmitic acid and myristic acid and their mixtures.

The petrolates are advantageously used in admixture with oils, liquid at room temperature (20 ° C).

Of the listed oils, the most extensive aromatic-free hydrocarbons and aliphatic fatty acid esters are preferred, in particular those of sections 1.1.2, 1.1.3 and 1.1.4 and in particular aromatic-free and aromatic-poor white spirits, isoparaffinic oils (1.1.3) and mineral oils (1.1.4) to be preferred.

A particular aspect of the invention consists in that c) is a mixture of at least two oils, in particular a mixture of an oil c1) and an oil cz), which are selected in such a way that the 0 / W-EHLB value of the oil c1) is greater than the O / W-EHLB value of the mixture of the oils c1) + cz). The O / W-EHLB value denotes the optimum HLB value for a hypothetical surfactant required for this oil or oil mixture, in order to produce a stable oil-in-water emulsion; see e.g. "Cosmetics, Science and Technology", published by John Wiley and Sons (2nd edition, vol. 3, 1974), pp. 602-607, or Philip Sherman 'Emulsion Science ", Academic Press, London and New York, 1968, p. 146-147, or also Paul Becher "Emulsion, Theory and Practice", 2nd edition, 1965, American Chemical Society, Mnograph Series no. 162.

Preferably, the 0 / WHEHLB value of the oil c 2) is less than the value of the oil c1).

Preferred oils c1) have a 0 / W-EHLB value in the range 10 to 15; such oils have been listed among those listed above, in particular those listed in sections 1.1.1, 1.1.2, 1.1.2 and 1.3. Preferred oils cz) have an O / WfEHLB value from 7 to 10; such oils are, among those listed above, in particular those listed in sections 1.1.4, 1.1.5, 2 and 3.

In addition to the surfactant b), the compositions of the invention may also contain non-ionic surfactants; these are expediently lipophilic.

Advantageously, the compositions according to the invention thus contain d) a lipophilic, preferably oil-soluble, non-ionic surfactant.

This component d) can be a uniform surfactant or even a mixture of lipophilic resp. oil-soluble, non-ionic surfactants. Suitably component d) is a W / O (water-in-oil) emulsifier, i.e. a surfactant which is capable of producing a W / O emulsion with at least a part of the oils c) in the presence of water.- The non-ionic surfactants d) are advantageously water-insoluble or only dispersible in water and have as WIO emulsifiers advantageously an HBL value § 8, preferably between 3 and 8; especially preferred, the HBL value is between 4 and 7. If d) consists of a mixture of non-ionic lipophilic surfactants, then the individual components of this mixture d) may also have different HBL values, and are then used in such relative amounts that the average HBL value of this surfactant mixture advantageously is § 8 and preferably lies between 3 and 8, in particular between 4 and 7. 10 15 20 25 30 35 13 458 526 j W As component d), ie. as lipophilic, preferably oil-soluble, non-ionic surfactants are generally common compounds, essentially those having at least one lipophilic carbon hydrogen residue, advantageously having at least 9, preferably 9-24 carbon atoms and at least one non-ionic hydrophilic residue , which is advantageously an optional propylene glycol moiety containing mono- or polyethylene glycol residue and / or a residue of a higher polyol (eg glycerol, mannitol or sorbitol); these lipophilic resp. oil-soluble surfactants can also be referred to as hydrophobic surfactants and of hydrophobic surfactants can also be mentioned hydrophobic Pluronie types and Tetronics, in which a high proportion of polypropylene glycol can be described as lipophilic residue. In particular, the following categories of non-ionic surfactants can be mentioned: Mono- or polyoxetylation 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 fats or oils; resp. corresponding etherification and / or esterification products of mono- and / or polyethylene and / or propylene glycols.

Fatty acid polyol partial esters; non-ionic ethylene oxide / propylene oxide copolymers with a high proportion of propylene oxide units (Pluronie types) and ethylene oxide / propylene oxide addition products to ethylenediamine, with a high proportion of propylene oxide units (Tetronic types), which due to a high proportion of propylene oxide units ionic surfactants.

The polyol partial esters listed are advantageously di- or preferably monoesters of aliphatic polyols having 3 or more hydroxy groups, preferably of glycerol, mannitol or sorbitol.

Preferred non-ionic surfactants are generally ono- and / or polyoxetylation products of aliphatic alcohols, of alkylphenols and of aliphatic fatty acids, polyol partial esters of aliphatic fatty acids, mono- and / or dieters of mono- and / or polyethylene glycols with aliphatic alcohols and / or phenols as well as mono- and / or diesters of mono- and / or polyethylene glycols with aliphatic fatty acids.

The fatty acid residues present may generally be acyl residues of common alkyl carboxylic acids or alkenyl carboxylic acids, with alkenyl carboxylic acids advantageously being monoethylenically unsaturated acids. Alkyl residues as single lipophilic residues [such as e.g. in the following formula (XVIIL] advantageously contains at least 9 carbon atoms, preferably 9-24 carbon atoms, in particular 9-18 carbon atoms and may be linear or branched. In alkylaryl residues, as in the rest of the formula (a) below, the alkyl scheme contains If the lipophilic residue is an acyl residue of a carboxylic acid, it is advantageously a residue of a fatty acid, essentially an alkyl or alkenyl carboxylic acid, which is preferably linear or branched. advantageously has 9-24, preferably 12-20 carbon atoms, with lauric acid, myristic acid, stearic acid and oleic acid being particularly preferred.In the case of polyethylene glycol derivatives, in particular also those of the following formulas, these are generally average formulas, i.e. those in which the stated number of ethyleneoxy units is an average number.14 Of the non-ionic surfactants cited, the following formulas are particularly preferred: d R6- (O-CH2-CH2 + šOH (XVII) and _ (Rfcoašr (xvnn, wherein R6 represents C) 9-24 alkyl or alkenyl or a residue of the formula (RB (a) ,.

R7-CO- each time an acyl residue of an alkyl or alkenyl carboxylic acid having 12-20 carbon atoms, R8 C4-12 alkyl, a q-host residue of glycerol or sorbitol or a mono- or polyethylene glycol of the formula HO- (CH2- CH2-0%; - H (XIX), * p 1: in 6, q 1 or 2, or at sorbitol also 3, r 1 or 2 and s 1 to 10 wherein the number and length of the lipophilic residues and the number -CH -CH 2 -O groups are suitably selected in such a way that the HLB value of fs 458 526 of the non-ionic emulsifier or emulsifier mixture is between 3 and 8, preferably between 4 and 7.

Among them, in particular, the following formulas are preferred: R 9 - (O-CH 2 -CB 2 + E-OH (XX), R 5 (O-CH 2 -CH 2 + in - OH (XXI), R 10 -CO-Y (XXII) ) and R 10 -CO-O- (CH 2 -CH 2 -OsrCO-R 10 (XXIII), wherein R 9 is C 9-18 alkyl or alkenyl, R 10 -CO- an acyl residue of an aliphatic C 1-18 fatty acid, Y- a monovalent residue of sorbitol, glycerol or di-bis-tetraethylene glycol, t 2 to 3, k 3 to 5 and m _ 4 to 9.

The HBL value of the non-ionic surfactants can be calculated by a simple known formula, knowing the lipophilic residue, the hydrophilic residue and the number of ethyleneoxy and propyleneoxy units, respectively.

If the calculated value for a non-ionic surfactant is 2.5 or less, it is no longer considered a W / O emulsifier. If c) is a mixture of oils c1) and cz), then the surfactants d) and the oils are advantageously chosen in such a way that 0 / W-EHLB of the mixture c1) + cz) is as close as possible to the HBL value of d) but with advantage is not less than this.

Advantageously, the compositions according to the invention also contain e) water.

The polymers a) resp. the polymer salts thereof, which contain the anion of the anionic surfactant as a counterion are hydrophilic, i.e. they can absorb water or in the presence of water form a gel or sun, resp. is 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, together with the water, is finely dispersed in the oil (either as a suspension of the polymer with water or water (swollen polymer or additional aqueous polymer gel in oil, or as an emulsion of the aqueous polymer sol or the aqueous polymer solution in oil).

A special object of the invention is that the preparation additionally f) contains emzmed oil miscible, water-insoluble and non-self-dispersible, polar solvent, which alone does not exhibit any emulsifier properties, but lowers the surface tension water / oil. these solvents are generally polar compounds which have an extremely low HLB value, but which are still sufficiently polar to be deposited at the oil / water interface; advantageously these are water-soluble, aliphatic alcohols or phosphoric acid triesters or Pluronics.

The alkene compounds advantageously contain s-10 carbon units per nyarexi group and in particular the following can be stated: methyl-isobutylcarbinol, 2-ethylhexanol, isononanol, isodecanol and 2,4,7,9-tetramethyl-5-decyne-4,7- diol. Among the phosphoric acid triesters, tributyl phosphate, triisobutyl phosphate and tri- (butoxyethyl) phosphate can be mentioned in particular. Among Pluronics, the Pluronic L101 in particular can be mentioned.

A further object of the invention is a process for the preparation of the compositions according to the invention, characterized in that the anionic surfactant b) is combined with the polymer a) or with the corresponding monomer, before, during and / or after the polymerization, wherein the polymer resp. corresponding monomers are preferably present in the most finely divided form.

In the case of polymers of non-vinyl-like monomers, it is preferable to add the anionic surfactant to the polymer, which is present in the most finely divided form, (eg as an aqueous solution and / or as a dispersion in oil, preferably as W / O emulsion to the aqueous polymer solution).

In the case of polymers of vinyl-like monomers, it is an advantage when the polymerization takes place in a W / O emulsion and at least a part of the anionic surfactants is added already before the polymerization and / or before the addition of the cationic monomer.

A particular object of the invention is a process for the preparation of preparations according to the invention, which contains polymers a1) which are characterized in that, in order to form polymers a1), the required monomers are polymerized in the presence of anionic surfactants in W / O emulsion and optionally distills off water and] or oil and optionally adds additional additives a), b), c), d), e) and / or f).

The vinyl-like monomers are advantageously emulsified in the form of an aqueous solution in the presence of anionic surfactants and preferably also in the presence of non-ionic, oil-soluble surfactants d) in at least a part of the oil c), the water-soluble monomers and in in particular the cationic monomers are present in a molar excess relative to the anionic surfactants; the aqueous phase emulsified in oil optionally contains additional additives, such as conventional complexing agents, salts and acids and / or bases for pH adjustment. In a preferred process variant, the vinyl-like monomers intended for polymerization are added to the prepared W / O emulsion, which already contains anionic surfactant and optionally non-ionic surfactant, or additional common additives, or they are added for polymerization. the vinyl-like monomers to an aqueous dispersion (suspension and / or emulsion) or solution of the anionic surfactant, after which oil and optionally non-ionic surfactant and / or additional customary additives may be added; thereby, aqueous monomer phase dispersions can be produced in oil. Due to the presence of anionic surfactants in a monomer-containing W / O emulsion, the cationic monomers - or a part thereof - may, in particular under neutral to acidic conditions, exist in the form of less water-soluble, lipophilic surfactant salts, wherein the anion of the anionic the surfactant acts as a counterion to cationic monomers and a further object of the invention are these salts of cationic vinyl-like monomers, wherein the counterion (A1) constitutes the anion of an anionic surfactant, preferably a lipophilic resp. oil-soluble anionic surfactant; they preferably correspond to the formula I R1 I cH2 = c- (Kat (9) (A1 6) (xxIv).

Preferred salts of the invention are those wherein the cation is such as in formulas (II), (IV); (VI), (VIII), (XI) and (XII); particularly preferred salts of the invention are those of formulas (II), (IV) and (VI), wherein the counterions are those of the above-mentioned anionic surfactants A1 (-), in particular of hydrocarbon sulphonates, in particular of petroleum sulphonates.

Preferred monomer salts according to the invention correspond to the formulas' 03 Rz _ _ __ E) cu2 = <|: co Na- (cnz-æí- N: <3 (m1) (xxv) 111 R4 and in particular to Rz 9 ca = -co- O-cn -cH -NR (MÖ- (mn 2 T 2 2 ~ \\\\\ 3 R1 R4 Monomer salts according to the invention are preferably prepared by adding an excess of cationic monomers which do not contain a surfactant counterion. A special aspect of this object of the invention is the corresponding W / O emulsions which these monomer salts contain. In a particular embodiment of the preparation process for the polymer-containing preparations according to the invention consists in that a oily dispersion containing a hydrophilic cationic polymer (a), water (e) and a lipophilic or oil-soluble, non-ionic surfactant (d) but no anionic surfactant was added with a lipophilic, preferably insoluble, practically water-insoluble , anionic surfactant (b1), wherein (b1) is a sulf hydrogenated hydrocarbon, optionally in salt form, and the oil in the oily dispersion is an oil (c3), i.e. a water-immiscible hydrocarbon oil, in which the polymer (a) is not soluble, but with the water atomized therein. The polymers (a) here are preferably vinyl-like polymers (a1) as described. Suitable hydrocarbon oils (c3) are those described in subsection 1.1, of which those according to the corresponding subsections 1.1.1 to 1.1.4 in particular 1.1.3, 1.1.4 and above all white spirit are preferable.

The oily dispersions which contain (a1) together with (e). (c3) and (d) but none (b), are advantageously prepared by emulsion polymerization of the corresponding aqueous monomer solutions in oil and are prepared in the presence of an emulsifier (d) and optionally partial distillation of water.

The polymerization can be carried out in a manner known per se, (see, e.g., "High Polymers", vol. 9, 1955 "Emulsion Polymerization", publisher: Interscience Publishers Inc., New York) and the aqueous system may the constituents currently required by the invention contain customary additives, such as polymerization initiators (preferably compounds which, during thermal addition, form free radicals or a redox system), complexing agents (eg Na-EDTA), acids and / or bases for pH adjustment and / or metal salts, eg Naf and / or Ca 2+ salts, after inertization (ie displacement of oxygen by inert gas) and after addition of suitable polymerization initiators, the polymerization takes place. ionization polymerization or after combining anionic surfactants and cationic polymers, in particular after dilution with water, cationic groups in the corresponding salt form may also be present in the polymer. exotherm and takes place e.g. 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-. 80% by weight, preferably 30-65% by weight (based on the whole emulsion).

The polymerization can be carried out adiabatically or even isothermally; however, it is preferably carried out partially adiabatically, i.e. the temperature may rise to a limited extent by dosed addition of the initiator and / or by cooling the reaction mixture, advantageously to values of § 120 ° C, possibly under pressure; preferably the process takes place between 30 and 110 ° C. If a mixture intended for polymerization contains hydrolysable monomers (in particular esters or primary amides), such reaction conditions are suitably chosen that a hydrolysis to the undesired acids is avoided as far as possible.

With the surfactants intended for insertion according to the invention, very finely divided dispersions can be obtained even with a relatively small surfactant. By emulsion polymerization, very high molecular weights of the polymers can be obtained, so that a very wide range of molecular weights of the polymers is available, which also allows a very wide insertability of the preparations according to the invention.

The emulsion polymerization suitably takes place in the presence of at least a part of the oils c). For the emulsion polymerization, oils are suitably used in which at least a part, preferably at least SO% by weight, in particular in particular at least 80% by weight, is hydrocarbons, with the most extensive aliphatic hydrocarbons being preferred. The relative amounts of water and oil, as well as the concentration of the aqueous monomer solution, can vary widely, with on economic grounds preferably the most concentrated mixture used in the process; the W / O emulsion intended for polymerization contains at least a part of the surfactants b) [preferably h ')] and / or d) which is sufficient to produce a sufficiently stable W / O emulsion for the polymerization.

After completion of the polymerization, the resulting polymer-containing W / O emulsion can be added with additional additives - e.g. with additional components a), b), c), d) and / or e) and / or with component f) - and / or can the content of components c) and / or e) e.g. by distillation is reduced; these further modifications of polymer-containing W / O emulsions may in particular affect the properties of the preparations e.g. their stability and / or their dilutability with water. If the preparation is to contain, in addition to polymer a1), also other polymers a), the latter are preferably added after emulsion polymerization has been carried out.

If the preparation is also to contain component f), this is advantageously added as the last, resp. after completion of emulsion polymerization to the preparation; advantageously f) 1 is used with a little oil c) previously diluted form, possibly even larger amounts of oil c) can be used and / or the addition can take place together with f) resp. with its solution in oil c) and with even further additives a), b), d) and / or possibly e). If the preparation is to contain a mixture of oils c1) and cz), then the emulsion polymerization advantageously takes place in oil c1), which optionally contains c2); oil G2) resp. the possible remaining part of the oil oz) can, if necessary, be added after emulsion polymerization, possibly after distillation of the water, resp. of most of the water. The quantitative composition of the preferred compositions of the invention and, as described above, can be advantageously schematized as follows: The composition contains in 100 parts by weight of component a) I b) C) d) e) and parts by weight of component f).

The concentrations x and y preferably correspond to at least those required in order for the aqueous monomer-containing dispersion to remain sufficiently stable during the polymerization; x advantageously constitutes at least 0.5, advantageously 1-30, preferably 1.0-15, in particular 1.5-10. The above ratios of a) and b) relate to the components in question without regard to a corresponding salt formation in the numbers 100 for a) and x for b), but shall nevertheless include a possible salt formation of a) + b); z is advantageously 0-80, preferably 1-80, in particular preferably 2-30. The compositions according to the invention are advantageously oily and y is preferably 30-400, especially preferably 40-200. The content of water can vary within wide limits and are partial parts by weight of components by weight of components by weight by components of component 4 G ßa '<X also depends on the content of oil, ie. of y, and more specifically to the extent that the compositions according to the invention in the not yet water-dilute oily form, in case they contain water, preferably contain this in the discontinuous phase, i.e. the oil is the continuous phase and the aqueous phase is dispersed resp. emulsified therein. After the (inverse) emulsion polymerization, the water can be distilled off, advantageously azeotropically, whereby in theory the entire amount of water can be distilled off, ie. to u = 0, which in practice, however, is not preferable, since it is difficult to completely distill off the residual water which has caused swelling of the polymer; on the other hand, the polymer-containing W / O emulsion may optionally still be added with water, e.g. in the form of an additional W / O emulsion or in the form of an aqueous solution of a polymer a), so that the water content of the preparation can also be relatively high; u is advantageously 0-300. preferably 1-300, especially preferably 2-200. From an economic point of view, it is preferable not to distill all the water and the water content is advantageously 5 to 300, preferably 10 to 200. p. 10 15 20 25 30 35 458 526 22 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, wherein f) is inserted in as small amounts as possible, in particular in amounts less than the γ component f) is dissolved in component CLY: advantageously constitutes v 0-30, preferably 0-15.

The compositions according to the invention advantageously have the following composition: in 100 parts a) x = 1-30 y = 30-400 z = 1-80 u = 0-300 v = 0-30, (wherein v Å ï) 3 En particularly preferred composition of the compositions according to the invention is the following: in 100 parts a) x = x '= 1.5-10 y = y' = 40-200 z = z '= 2-30 u = u' å z- zoo v = v '= o-1s, and v' <The oily preparations according to the invention are dispersions which can have very different viscosities and also very thin liquid preparations can be prepared; then the viscosity (Brookfield rotational viscosity, measured in .LV viscometer) of the dispersions can vary e.g. between 5 cp (spider no. 2) and 10,000 cp (spider no. 4); preferably between 50 cp (spindle No. 2) and 5,000 cp (spider No. 4); the dispersions according to the invention are also stable, i.e. they can be stored for a longer time without change, or, when the dispersions are separated into layers, they can be brought to the original, regularly dispersed form by a simple stirring. In particular, the very good distributability in water resp. the dilutability with water of the compositions according to the invention, in particular the c) -containing preparations, and more particularly they can already be diluted very rapidly by simple addition of the preparations to water or of water to the preparations with stirring, or even ordinary diluents rates, which are common in the art and in the literature also often described, are used for a pre-dilution with water. Particularly suitable are diluents which operate with water pumps, ie. the polymer dispersion is pumped through a nozzle and the water through another nozzle in such a "chamber" that the water carries the dispersion at high speed, after which the mixture in various ways, e.g. over impact plates or walls or during use of high shear forces or by pumping in and out of "rest tanks" is redistributed in water. A particularly valuable process for diluting the dispersions according to the invention with water is characterized in that the dispersion is introduced through at least one nozzle (I) in such a way in a water flow that the water flow rewinds the nozzle (I), the volume flow of the water being higher than the volume flow of the dispersion and the velocity of the water so much higher than the velocity of the dispersion, that the dispersion is thus absorbed by the water flow, that the adhesion and / or cohesive forces in the dispersion are at least partially overcome, but that in the flow substantially no such high cutting forces it occurs that the molecules in the dispersion are thereby decomposed, that the product-water mixture is then accelerated through a restricted line and then retarded in an extended mixing zone, whereby acceleration and deceleration are carried out so often that the desired distribution of the product in the water is achieved and, after the dispersion and the water have come into contact with each other, the procedure is carried out without the use of filters or suction screens.

Particularly noteworthy is an apparatus (mixer) for carrying out this dilution process, which apparatus is characterized by a line (2) provided with a nozzle @ for feeding the viscous product, a line (:) for feeding water, a line (:) for acceleration of the mixture, a deceleration zone (5) and a line (6) for removing the product diluted with water. For the dilution with water, an addition in aqueous medium is desirable, e.g. a surfactant (in particular an O / W emulsifier), this can advantageously e.g. dosed in line C). the apparatus is preferably tubular and divided into chambers: the conduit C] for the supply of water is suitably arranged at one end of the apparatus coaxially therewith and the conduit (2) for feeding the dispersion is preferably arranged at a right angle to the conduit @ at the apparatus, and more particularly preferably in such a way that the nozzle CD is located as close as possible to the mouth of the line C) and advantageously such that the nozzle surface is located between the boundary and the center of the direct water jet. The first part of the device, ie. the chambers attached to the lines Q] and @, can also be referred to as "draw chambers", since the viscous product, from the nozzle Ü) of the exit of the water jet from @ @ is pulled along or rather drawn along. The nozzle @ can consist of a single opening, e.g. round opening or a slot, or may also be a plate with a plurality of heels (preferably 1 to 20 openings with a diameter of 0.2 to 5 mm each time), which is particularly preferred with more highly viscous products. in that through the nozzle already a first distribution of the product takes place. The water flow at the exit from the line @ may be laminar to turbulent, but is preferably turbulent; the volume flow and the velocity of the water are suitably selected in operation to the product intended to be diluted, with generally the highest possible turbulence and velocity of the water being preferred; The Reynolds number at the exit from the tube @ advantageously has values between 10,000 and 100,000, preferably between zs ooo and vs ooo. In the other half of the drawing chamber, near the end wall, the line Q] is arranged, which may be a pipe or even a hose (most simply a hose), the inner cross section of which is smaller than the inner cross section of the drawing chamber, whereby the mixture of water and product therein are accelerated; advantageously, the inner diameter of the conduit @ is not less than half of the inner diameter of the conduit @ and not greater than half of the inner diameter of the traction gun resp. the mixing shaft; preferably the inner diameter of the line GQ 'is equal to that of the line in SO%; particularly preferably the lines Q) and (4) have the same inner diameter. The inner volume of the connecting lines @ is advantageously not larger than the inner volume of the drawing chamber (R): preferably the connecting lines @ are as short as possible (inner volume 4%, preferably fw). The nozzle can also be fitted with more than one nozzle for pumping in the viscous product; for example in the case of vertical arrangement of the mixer (ie when the dilution water is pumped through the pipe @ vertically from above and downwards or 'from below and upwards in the mixer) several nozzles can be arranged radially around the axis near the mouth of the line @, or e.g. with horizontal arrangement of the mixer, several nozzles can also be applied one after the other. The horizontal arrangement of the mixer (see Fig.) Is to be preferred and the pumping of the dispersion through a single tube C] is simplest and preferable. After the diluted mixture is accelerated through the line @, it flows through the deceleration zone @ resp. into the mixing gun (M), where the mixture is preferably retarded, preferably during the formation of vortices: from the mixing chamber (M) the mixture flows out after a further acceleration through a line (:) or through a further line C) (during repeated acceleration). The ratio of the inner diameter of the tube @, the line Qi] resp. the line @ or (I) to the inner diameter of the (cylindrical) chamber (R) resp.

(M) is preferably 1: 3 to 1:20.

A schematic representation of such a mixer with horizontal arrangement of the chambers has been illustrated in Fig. 1. In Figs. 1.1 and 1.2 the essential constituents have been prepared as non-profit fragments, and more specifically pumped in Fig. 1.1 at the end (A) of the mixer through the tube C] water and in the connected part (B) is pumped through the tube (:) and the nozzle (:] the viscous product: part (B) may be recurring, preferably however (B) a single part: i part (C) the line (2) is fitted and part QQ in the drawing forms a retardation zone, the essential part (C) may be recurring, advantageously part (C) occurs 1-10 times, preferably 2-6 times; the existing @ lines may have the same diameter or the diameter may also vary, eg increase regularly, when, for example, the viscosity of the diluted product increases sharply with finer distribution; it is easiest when all existing lines (:) mutual Fig. 1.2 has the same apparatus as in fig 1.1 has been reproduced, where only the division instead of acceleration and deceleration zones in the chambers has been clarified, ie. (R) constitutes the drawing chamber, which consists of the parts (A), (B) and (G1) and (M) is a mixing chamber, which may be recurring [as part (C) in Fig. 1.1]. The diluted product is removed by line (Ö (or by line @ from the last chamber); the line (:) (or line (:) from the last chamber) can have the same diameter as the lines QD (resp. last of the lines (:) or even different diameters, eg a slightly larger diameter, eg up to 50% larger), all still in this line an acceleration of the diluted product takes place. preferred arrangement of the chambers has been shown in Fig. 2. the apparatus can be built in the most different sizes as required, so for example the internal volume of each individual chamber can vary from a few if up to about one m3, the corresponding pipes, nozzles and connecting pipes being correspondingly built in a proportionate manner, the internal volume of the chambers (R) and (M) can, when desired, vary up to 150%, however, preferably the chambers in question have compared with each other the same inner volume.The mixing chambers- are advantageously built p in such a way that they are mounted and disassembled as special elements which can be connected to each other by hoses [I, so that in one and the same apparatus the number of mixing chambers can be varied as required; it is also expedient when the individual lines Q), @, @ and @ resp. * ®, e.g. through nozzles, are arranged in such a way that they can be disassembled or even exchanged for others of different diameters as required; the nozzle (I) is also advantageously attached to the pipe C in question in such a way that it can be replaced as required, in particular depending on the viscosity of the polymer dispersion.

The mixer in operation, that it is not actually those according to the invention which is suitably kept in such a way practically filled with liquid and consequent different liquid flows bounce against parts or walls of the mixer, but that a vortex is formed in the liquid.

Depending on the solubility of the product resp. dispersibility and possible swelling effect in water (or increase in viscosity), the number of mixing chambers and the diameter of the various pipes, respectively. pipes, as well as the outlet velocity of the water is correspondingly selected and optimized. A measure of the acceleration and deceleration effect at a given Reynolds number of the inflowing water and at a given apparatus is the pressure drop between inflowing water and effluent diluted product; the minimum required pressure drop to achieve a good distribution resp. dilution, can also vary depending on the product used and advantageously has a value of 0.2 bar; in the case of a medium-sized mixer (the internal volume of the mixer of the order of 10-3 to 10 "* m3) is preferably prepared in this way, see: pressure pressure is not less than 0.5; the upper limit of the pressure drop is determined by the resistance of the apparatus; good dilution effects are achieved with a mixer of medium size at a pressure drop g S bar or even g 2.5 has and with well-dilutable products, even already 10 15 20 25 30 35 'in 21 458 526 at a pressure drop § 1.5 bar Although better dilution effects are achieved at the highest possible pressure drop (ie a faster atomization), it is preferable on apparatus and also on economic grounds, when the inlet pressure of the water is kept as low as possible. mixers of medium size are obtained in an area for the pressure drop.between 0.5 and 2.5 bar, in particular in the range between 0.6 and 1.5 bar.The mixer according to the invention can be operated very quickly and ready-to-use diluted preparation can already be obtained in a few seconds.

Due to the very fast dilution with water of the compositions according to the invention, several large-scale, continuously carried out processes, in which cationic polymers are used, can be carried out very rationally and with optimum dosing speed. It is also particularly noteworthy that the compositions according to the invention can have a very high concentration of cationic polymers; in addition, the biological eliminability of the preparations can also be stated. The preparations according to the invention are characterized by their dilutability with water and distributability in water, and the invention comprises such preparations in arbitrary concentrations, insofar as they are still dilutable with water resp. the polymers are soluble or dispersible in water resp. are dissolved or dispersed: in particular refers to both higher concentrated preparations, in particular those with at least 10% by weight of cationic polymer, as well as pre-diluted preparations, in particular those containing at least 0.001% by weight, preferably at least 0.1% by weight of cationic polymer.

The compositions of the invention are useful in all fields of the art in which cationic water-soluble polymers are used, in particular they are useful as flocculants and a further object of the invention is the use of the compositions of the invention as flocculants, preferably as retention and dewatering agents for paper. and as a flocculant for aqueous sludges, in particular for digestate sludge and fresh sludge in municipal treatment plants. Furthermore, the object of the invention is also a process for the production of paper, which is characterized in that a preparation according to the invention is used as retention and / or dewatering agent.

In the production of paper during insertion of the compositions according to the invention, a particularly homogeneous leaf formation can be observed. The required concentration of the preparation for the current use is of course directed to the concentration of active substance (polymer) for the current flocculation.

The mixer described above can be connected to any plants in which corresponding, water-diluted products must be metered in continuously, and in particular those plants in which dilute water-soluble or at least water-dispersible high polymers must be metered in. as flocculants in wastewater reprocessing or wastewater treatment, in papermaking (in particular as retention and / or dewatering agents), in slurry of drilling sand and / or other minerals in sand or colloidal form or in residual oil extraction in the mineral oil industry.

Due to the rapid fine distribution of the polymers in this dilution process and with this apparatus, corresponding dilute solutions or dispersions can be obtained, also without a residence time resp. receptacles must be connected; corresponding mixers according to the invention can be connected directly to the plant.

A further object of the invention is precisely the use of the mixer according to the invention as a dilution station for polymer dispersions according to the invention in plants in which the corresponding products must be used as flocculants in diluted form, in particular in papermaking and wastewater treatment plants. In the following examples, parts denote parts by weight and percent by weight; the temperatures are given in degrees Celsius. The products used are, unless otherwise stated, common commercial products. Example 1. 143.5 parts of emulsifier (B1) are mixed with 800.0 parts of water to form a very fine, opalescent emulsion. Then, to form the calcium salt of (B1), 8.2 parts of calcium chloride are added. A strong precipitate can be immediately observed, which corresponds to the formation of the water-insoluble (oil-soluble) calcium sulfonate.

Then 440.0 parts of white spirit (C1) are added with stirring. 10 15 20 25 30 35 29 458 526 A water-in-oil emulsion is formed, which is stabilized by the addition of 99.5 parts of emulsifier (D1). This water-in-oil emulsion was added in the order given with 353.0 parts of a 75% aqueous methacryloyloxyethyltrimethylammonium chloride solution, 454.0 parts of acrylamide, 1.4 parts of ethylenediaminetetraacetic acid disodium salt, 0.7 parts. ferrous sulfate and 0.7 parts of tert-butyl hydroperoxide. The pH of the aqueous phase is about 3.0. The resulting dispersion is then inertized with nitrogen and heated to 35 ° C. As soon as this temperature is reached, a dropwise addition of an air-free solution of 2.7 parts of sodium thiosulphate in 50.0 parts of water is started. The addition is carried out over the course of 8 hours, the temperature being kept between 35 and 40 ° C by cooling.

After the addition of the sodium tics sulphate solution, the polymerization reaction is complete. A stable, fine thin-liquid polymer-containing dispersion is obtained, which has a viscosity of 1000 cp (Brookfield, spindle 3, 60 rpm). The product is very well dilutable with water: about 30-40 s after the addition to cold water, the maximum viscosity with a 1: 200 (= 0.5%) dilution with water has already been achieved. The viscosity of a freshly prepared 1: 100 diluted (= 1%) aqueous preparation is about 500 cp (Brookfield, spider 3, 60 rpm).

Example 2. 454.0 parts of acrylamide, 353.0 parts of a 75% aqueous methacryloyloxyethyltrimethylammonium chloride solution, 1, ¶ parts of ethylenediaminetetraacetic acid disodium salt, 0.7 parts of ferrous sulphate, also 9.8 parts of calcium chloride are added in the specified order, while stirring, to 600.0 parts of water.

The resulting solution is then mixed with a solution of 52.0 parts of emulsifier (B1) and 80.0 parts of emulsifier (D1) in 600.0 parts of white spirit (C1). A water-in-oil emulsion is formed with a pH (aqueous phase) of 3.0, which is then inertized with nitrogen. * Then 0.7 parts of tert-butyl hydroperoxide are added to initiate the polymerization reaction and then an airborne solution of 1.1 parts of sodium thiosulphate in 12 parts of water. A strong exothermic reaction occurs immediately, with the temperature rising from room temperature up to 90 ° C despite slight cooling. A thin liquid, polymer-containing, water-readily dilutable dispersion is obtained.

Example 3. 24 parts of emulsifier (Bi) are mixed with 480 parts of water, whereby a very fine opalescent emulsion is formed. Then 564 parts of a 75% aqueous methacryloyloxyethyltrimethylammonium chloride solution are added to form the corresponding methacryloyloxyethyltrimethylammonium petroleum sulfonate. Then add in the order indicated, with stirring in addition 408.30 parts of acrylamide 1.43 parts of ethylenediamine tetraacetic acid disodium salt 0.77 parts of ferrous sulfate, 480.0 parts of white spirit (C1) 30.0 parts of emulsifier (D1) 30, 0 parts of emulsifier (D2) 4.8 parts of calcium chloride 1 0.6 parts of tert-butyl hydroperoxide Then the resulting dispersion is inertized with nitrogen and heated to 30 ° C. As soon as this temperature is reached, a dropwise addition of an air-free solution of 2.97 parts of sodium thiosulphate in 42 parts of water is started. The addition takes place over the course of 8 hours, during which the temperature rises to 50 ° C. A fine dispersion-containing dispersion is obtained, which is well dilutable with water, Example. 500 parts of the preparation obtained according to Example 1 are mixed with 10 parts of white spirit (C1) and 10 parts of emulsifier (BZ) with stirring. It is then evacuated at 26 mbar and the temperature is raised from room temperature to 40 ° C, whereby about 200 parts of water are regularly distilled off by means of a water separator. A fine, stable polymer-containing dispersion is formed, which is well dilutable with water.

Example 5 The procedure is as described in Example 1 and to the obtained preparation is added 10% (by weight of the preparation obtained according to Example 1) of a 20% preparation according to Example 3.1 according to French patent 1 S83 363, under stirring. ring, whereby a stable W / O emulsion is obtained. 10 15 20 25 30 35 458 52-6 31 Example 6.

Part 1: dispersion (1). 454.00 parts of acrylamide, 353.00 parts of a 75% aqueous solution of methacryloyloxyethyltrimethylammonium chloride and 800.00 parts of water are introduced into a sulfonation flask and stirred. After the acrylamide has dissolved, 1.43 parts of ethylenediamine tetraacetic acid disodium salt as well as 0.72 parts of ferrous sulfate are added to the reaction solution and the pH is adjusted by adding about 0.10 parts of 30% sodium hydroxide solution of 3. 0. A solution of 143 parts of emulsifier (D1) in 440 parts of white spirit (C2) is then allowed to flow to the monomer solution with vigorous stirring. A milky water-in-oil emulsion is formed, which is then evacuated 5 times to a pressure of 26 mbar and each time equalized with nitrogen. A strong nitrogen stream is then passed through the emulsion liberated from the air at a high stirring speed. Then 0.67 parts of tert-butyl hydroperoxide are added to the cold reaction solution and heated to 35 ° C. As soon as this temperature is reached, 50 parts of a solution of 2.70 parts of sodium thiosulphate in 50.00 parts of water are added dropwise over the course of 5 hours to the monomer emulsion. During the thiosulfate addition, the exothermic polymerization reaction sets in, keeping the temperature at 36-38 ° C by light cooling. The whole is then allowed to react for a further 2 hours at 35 ° C and then cooled to room temperature, the nitrogen supply is stopped and discharged.

Part 2: addition of (b1). 200 parts of the dispersion (1) prepared according to part 1 are added with 20 parts of white spirit (C2) as well as with 20 parts of a 30% mineral oil solution of petroleum sulfonate (B1) in the form of the calcium salt. A viscous product is obtained which, however, despite the high viscosity, when added to water (eg 4 parts of product to 396 parts of water) can be rapidly diluted.

Part 3: preparation of (b1).

The detroleum sulfonate (B1) in the form of the calcium salt is prepared by treating a 20% aqueous emulsion of (B1) (sodium salt) with an excess of CaCl2, filtering off the separated (81) calcium salt, washing with water and drying under vacuum at 60-70 ° C. 1: 4 10 15 20 25 30 458 526 32 in Example 7. g 200 parts of dispersion (1) according to Example 6 (part 1) were added with 25 parts of a solution of 10 parts of a paraffin sulfonate (B3) in the form of the calcium salt in 80 parts of white spirit (C2) and 30 parts of mineral oil (C31. The resulting mixture can be very well diluted with water. The calcium salt of the surfactant (B3) is prepared analogously to that described in Example 6, part 3, instead of (B1) the corresponding amount (B3) is inserted.

Example 8. 200 parts of dispersion (1) according to Example 6 (part 1) were added with 30 parts of a solution with the following percentage composition: 14.3% petroleum sulfonate-Na salt (B2) 57.1% mineral oil ( C3) 28.6% of an SO% solution of triisobutyl phosphate (P1) in isobutanol.

A viscous product is obtained, which can be easily diluted when added to the water.

Example 9.. 2210 parts of the polymer-containing emulsion prepared according to Example 1 are evacuated after the addition of 330 parts of mineral oil (G3) and 330 parts of petrolatum (04) with stirring at 26 mbar and heated for about 6 hours up to 40 ° C, with 860 parts of water regularly distilled off using a water separator. Together with the water, a small amount of oil distills, which accumulates in the water separator on the water surface and is regularly returned to the reaction vessel. A very fine, stable, slightly viscous dispersion is obtained, which can be diluted about as well with water as the product according to Example 1.

Example 10.

A nitrogen inert dispersion consisting of 960.0 parts of water 816.6 parts of acrylamide 1128.0 parts of a 75% aqueous methacryloyloxyethyltrimethylammonium chloride solution 2.9 parts of ethylenediamine tetraacetic acid disodium salt 1.5 parts of ferrous sulphate 9.1 parts calcium chloride 48.0 parts emulsifier B1 60.0 parts emulsifier D1 10 15 20 25 30 35 J 3 458 526 60.0 parts emulsifier D2 960.0 parts white spirit (C1) which is adjusted to pH 3 with a little sulfuric acid To initiate the polymerization reaction was first added 1.2 parts of tert-butyl hydroperoxide. Then a dropwise addition is initiated; of an airborne solution of ¿6.5 parts of sodium thiosulphate in I 20.0 parts of water.

The addition takes place over the course of 8 hours, during which the temperature rises to about 48 ° C despite cooling. After the thiosulfate addition, the polymer-containing emulsion is added with 165.7 parts of mineral oil (C3) as well as 27.7 parts of emulsifier (D3) and then distilled off under vacuum (20-26 mbar) and at an internal temperature of not more than 50 ° C by means of a water separator. about 1186 g of water. A very fine thin liquid dispersion is obtained, which after distilling off the water is still added with 157.5 parts of olive oil (Cs) and 157.5 parts of 2-ethylhexanol (F2). The dispersion containing olive oil and 2-ethylhexanol can be instantly diluted in water.

Example 11.

It is carried out analogously to Example 10, except that 2-ethylhexanol (FZ) is replaced by triisobutyl phosphate (F1).

Example 12.

It is carried out analogously to Example 10, except that 2-ethylhexanol (P2) is replaced by tributoxyethyl phosphate (F3).

Example 13. The procedure is analogous to Example 10, except that 2-ethylhexanol (F2) is replaced by 2,4,7,9-tetramethyl-5-decyn-4,7-diol (P4). Example 14. 43.5 parts of emulsifier (B1) are mixed with 834.0 parts of water to form a very fine, opalescent emulsion. Then, to form the calcium salt of (B1), 8.2 parts of calcium chloride are added. Then, with stirring, 557.0 parts of acrylamide, 216.0 parts of a 75% aqueous methacryloyloxyethyltrimethylammonium chloride solution, 1.4 parts of ethylenediaminetetraacetic acid are added. acid-disodium salt as well as 0.7 parts of ferrous sulphate, forming a cloudy solution. Then another 400.0 parts of isoparaffinic solvent (C6), 40.0 parts of mineral oil (C3), 100.0 parts of emulsifier (D1) and 13.0 parts of emulsifier (B2) are added. 10 15 20 25 30 35 458 526 á4 A water-in-oil emulsion is formed, which is inertized with nitrogen.

Then, to initiate the polymerization reaction, first 0.7 parts of tert-butyl hydroperoxide and then 6.0 parts of a solution of 2.7 parts of sodium thiosulfate in 50 parts of water are added dropwise. An exothermic reaction takes place, whereby the temperature rises to ss ° c despite cooling.

Example 15.

The procedure is as in Example 14 with the following modifications: 709.0 parts of water are used instead of 834.0 parts, 183.3 parts of acrylamide are used instead of 557.0 parts, 714.0 parts of 75% methacryloyloxyethyltrimethylammonium chloride solution are used. instead of 216.0 parts the temperature rises under adiabatic conditions up to about 43 ° C.

After the polymerization, another 33 parts of Pluronic L101 (FS) and 165 parts of fatty acid methyl ester mixture (C7) are added.

Example 16.

The procedure is as in Example 14 with the following modifications: - 160.0 parts of mineral oil (CB) are used instead of 40.0 parts of mineral oil (C3) - the temperature is kept between 35 and 40 ° C.

Example 17. 43.5 parts of emulsifier (B1) are mixed with 800.0 parts of water to form a fine, opalescent emulsion. Then 8.2 parts of calcium chloride, 363.0 parts of acrylamide, 124.0 parts of diallylamine, 353.0 parts of a 75% methacryloyloxyethyltrimethylammonium chloride solution, 131.0 parts of hydrochloric acid (34%) are added in the order indicated for pH adjustment. the value of 3.0, 1.4 parts of ethylenediamine tetraacetic acid disodium salt and 0.7 parts of ferrous sulphate. A homogeneous monomer solution is formed, which is then added with 400.0 parts of white spirit (C1), 40.0 parts of mineral oil (C3) and 100.0 parts of emulsifier (D1). A fine emulsion is formed, which is inertized with nitrogen. Then, to initiate the polymerization reaction, first 0.7 parts of tert-butyl hydroperoxide and then 160.0 parts of a solution of 2.7 parts of sodium thiosulfate in 50.0 parts of water are added dropwise. An exothermic reaction occurs, with the temperature rising to es ° c under adiabatic conditions. 10 15 20 25 30 35 35 458 526 Exemgel 18.

The procedure is as in Example 2 with the following changes: - instead of 52.0 parts of emulsifier (81) 29.0 parts are used here - instead of 80.0 parts of emulsifier (D1) 49.0 parts of emulsifier (D3) are used and 65.0 parts of emulsifier (D4).

Exeggel 19. 43.5 parts of emulsifier (B1) are mixed with 800.0 parts of water to form a fine, opalescent emulsion. Then first 8.2 parts of calcium chloride and then 454.0 parts of acrylamide, 353.0 parts of a 75% aqueous methacryloyloxyethyltrimethylammonium chloride solution, 1.4 parts of ethylenediaminetetraacetic acid disodium salt and 0.7 parts of iron (III) are added. Sulphate. The resulting solution is then mixed with 400 parts of white spirit (C1), 40.0 parts of mineral oil (C31, 100.0 parts of emulsifier (DT) and 54.0 parts of emulsifier (B2). A water-in-oil is formed. emulsion, which is inertized with nitrogen, then 0.7 parts of tert-butyl hydroperoxide are then added dropwise to initiate the polymerization reaction, and then 45.0 parts of a solution of 2.7 parts of sodium thiosulphate in 50 parts of water. exothermic reaction occurs, whereby the temperature rises to 90 ° C for about 90 minutes.

Example gel 20. 43.5 parts of emulsifier (B1) are mixed with 600.0 parts of water.

Then 8.2 parts of calcium chloride, 454.0 parts of acrylamide, 1.4 parts of ethylenediamine tetraacetic acid disodium salt, 0.7 parts of ferrous sulphate, 400.0 parts of white spirit (C1), 40 are added in the order indicated. , 0 parts mineral oil (C3), 100.0 parts emulsifier (D1) and 13.0 parts emulsifier (82). A water-oil emulsion is formed, which is then inertized with nitrogen and added with 0.7 parts of tert-butyl hydroperoxide as well as with 1.0 part of a solution of 2.7 parts of sodium thiosulphate in 50.0 parts of water. An exothermic polymerization reaction occurs immediately, with the temperature maintained at about 60 ° C. Shortly before the exothermic reaction has ceased, a dropwise addition of an air-free solution of 265.0 g of methacryloylethyltrimethylammonium chloride in 288.0 parts of water is started, the temperature rising again and being kept at 55-60 ° C by cooling. After the exothermic polymerization reaction, the mixture is stirred for a further 1 hour at 55 ° C and cooled to room temperature (20 ° C). 10 15 20 25 30 35 458 526 Example 21, The procedure is as in Example 15 with the following changes: 0 11.00 parts of emulsifier (B1) is inserted 1 instead of 43.50 parts 25.00 parts of emulsifier (D1) are inserted instead of 100.00 parts 3.25 parts emulsifier (82) are used instead of 13.00 parts after the polymerization are added iggg (FS) and (G7).

Exeggel 22.

The procedure is as in Example 16 with the following changes: - 21.75 parts of emulsifier (B1) are inserted instead of 43.50 parts - 50.00 parts of emulsifier (D11 is inserted instead of 100.00 parts - 6.50 parts of emulsifier ( B21 is used instead of 13.00 parts.

Used emulsifiers êæsšsesealë fl = 36 62% solution of a petroleum sulfonate (monosulfonate) in the form of the sodium salt of molecular weight 440-470 in mineral oil. §¶Glg§§g§_1§2): 60% solution of a petroleum sulfonate (monosulfonate) in the form of the sodium salt with a molecular weight 480 in mineral oil. _§Gg} ¶§§g§_j§3): Secondary n-alkane sulfonates produced by sulfoxidation of paraffins in the form of sodium salts, in which the alkane residue on average has the following composition: c13-c15 = 58% cw-c fl = 39% > C17 <3 z <C13 <1% gguglqgggg 911: c1 znzs-æocazcnza-z-oa HLB = 6,5 §mglg§§9g_1Q2): C18H35- + OCH2-CH2 + §-OH HLB = 6,5 §mgl¶ a§gg_1Q3): sorbitan monooleate HLB = 4,0 '§1¿ \\ _ 1_l_ga_1f_: 91_r_11_> ¿): Mixture of c17H33c0 (0cH2CH2) 6'5 0-co-c171-133 and Cj7H33CO (OCH2CH2) 6¿s OH molar ratio 1: 1: average HLB = 7.0 Oils used ¶§§§e_§g§§it_¿§1): aromatic-free terpenaline, boiling range 193-247 ° C, average molecular weight 173. ¶§itg_§Qirit_l§2): aromatic low terpenaline, boiling range 190-ZSOOC, average molecular weight 180, aromatic content 0.5%. 10 15 20 25 30 35! Iae§el9lie_l93> = 2e§selesum_l§4> = 9l¿! 9lie_l§5) = š§9e§§ëš§äa_196> = Ess: ëxëeæe§xle§§§§ël맧n ¿N¶_l97) = M; n§§el9li§_i§8> = 37 458 526 partially unsaturated mineral oil with the following specifications: density 0,85 - 0,95 aniiinpunkt 7o-so ° c iodine value 20-30. petrolatum with solidification point = 50-85 ° C and sex penetration at 25 ° C = 160-180 isoparaffinic oil with: xok range 210-2eo ° c aniline point ss ° c isoparaffin content 80% density 0.78 methyl esters of C12 to C20 fatty acids with the following specifications fictions: density 0,87-0,90 acid number 1,12 saponification number 190-200 iodine number 100-110 neo-oxytal 40-so hydrocarbon mixture with the following specifications: density 0,85-0,95 aniline point 9s ° c viscosity (2o ° c) 30 cp Solvent used (f) triisobutyl phosphate (50% solution in isobutanol) 2,4,7,9-tetramethyl-5-decyn-4,7-diol (P2) 2-ethylhexanol (F3) tri-butoxyethyl phosphate (P4 (FS) "a Pluronic L101: ethylene oxide-propylene oxide copolymer having a molecular weight of 3610 and 10% by weight of ethylene oxide units.

Dilution Exam Gel I.

A mixer is used, in which a drawing chamber and a mixing chamber are arranged horizontally one after the other and all represent a cylinder whose axis lies horizontally; the internal diameter of the individual chambers is 110 mm and the internal volume of each chamber is 2.5.1o “3 m3. The inner diameter of the water supply pipe for the connecting hoses between the drawing chamber and the mixing chamber and between the mixing chambers as well as for the line for removing the diluted product is 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 time.

In the mixing chamber of the mixer, a polymer nozzle with an opening of 2 mm diameter, 10 l / h of the preparation according to Example 1 (polymer emulsion) is pumped by pulse, with a frequency of 50 s-1 and through a water nozzle with an opening of 15 mm diameter 2000 l / h water. the velocity of the water at the nozzle opening is 3.2 m / s (= Re 47000) and rewinds the entire polymer nozzle.

The diluted product coming out of the mixer constitutes a ready-to-use aqueous solution of the polymer and is ready for use in papermaking.

Dilution Example II.

It is carried out as described in Example 1, but a mixer according to Fig. 2 (and Fig. Za) is used, wherein the polymer nozzle is each 1 mm in diameter and 5 l / h polymer emulsion 1 is pumped into the mixer. The 6 openings of the dilute product obtained from the mixer constitute a ready-to-use aqueous solution of the polymer and are ready for use for papermaking.

Application example A.

A 2% aqueous pulp with the following dry matter composition was used: 100 parts bleached sulphite pulp 20 parts kaolin 3 parts resin adhesive 2 parts aluminum sulphate For the leaf formation on a Rapid-Köthen leaf former, 250 ml of sample material is mixed with 5 resp. 10, 15 and 20 ml of a 0.0125% aqueous dilution of the product of Example 1 as well as with 750 ml of dilution water. After a stirring time of S s at 250 rpm, the material / water mixture is transferred to the filling chamber of the blade former (Rapid-Köthen system), whereby 3 liters of water are present in the filling chamber. After a holding time of 20 s, the blade is formed by acting on the suction valve. After drying and conditioning the test sheets, these are ashed. The ash content is related to the inserted filling material and is expressed in% retention. 10 15 20 25 30 39 'in 458 526 The results are summarized in the following table; the values given for% ash and% retention are each time averages for two determinations.

Additive amount in ml Concentration flock%% 0,0125%% * in% Ash Retention solution (shaved on dry paper material) 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. 5 - 8.51 51.1 * (polymer emulsion) Application Example B. 200 parts of a digestate slurry with 5% dry matter content are first mixed with w parts of a 0.23% aqueous dilution of the preparation prepared according to Example 1 and reconstituted. then 10 s by means of a "Triton" stirrer at a speed of 1000 rpm. Then the sludge suspension is immediately filtered by means of a pulp filter and the average value of the volume of the filtrate is determined after 30, 60, 90, 120 and 180 s._ w Volume average 0 1.5 volume parts 13 15.3 - "- 15 40.4 -" - 17 49,1 - "- 19 81,9 -" - In a manner analogous to that described in application examples A and B, the products according to examples 2-22 can be used.

Claims (10)

458 526 = HD PATENT REQUIREMENTS Water-dilutable polymer-containing and teneid-containing preparations, characterized in that they contain a) a hydrophilic cationic polymerate, and b) an anionic teneid, the molar proportion of anionic surfactant b) not exceeding the molar the proportion of cationic monomer units of polymer a) and wherein the cation of the polymer and the anion of the anionic teneide may be joined together to form a salt. Preparation according to claim 1, characterized in that. that the further essential components contain c) a water-immiscible oil, in which the polymer is not soluble, but finely divided therein and optionally d) a lipophilic resp. oil-soluble, non-ionic teneid and / or 'e) water optionally E) a polar solvent mixed with oil, water-insoluble and non-self-dispersing, polar solvent, which alone does not show any emulsifier properties, but which reduces the surface tension water / oil. Preparations according to Claim 1 or 2, characterized in that c) is a mixture of oils ci) and oz), which is selected in such a way that the O / W-EHLB value of 61) is greater than the 0 / W-EHLB value of the mixture ei) + czä. Preparations according to claims 1-3, which contain at least 0.001% by weight, advantageously at least 0.1% by weight, preferably at least 10% by weight of component a). 5.; Preparation according to one of Claims 1 to 4, characterized in that a) is a polymer of vinyl monomers and b) is a sulfonated hydrocarbon. Process for the preparation of preparations according to Claim 1, characterized in that the anionic surfactant b) is combined before, during and / or after the polymerization, with the polymer a) resp. with corresponding monomers. Process according to Claim 6 for the preparation of a composition according to one of Claims 1 to 4, characterized in that an oily dispersion containing a hydrophilic cationic polymer (a), water (e) is added; ) and a lipophilic resp. oil-soluble, non-ionic teneid (d), with a lipophilic resp. oil-soluble, substantially water-insoluble, anionic teneid (b1), wherein (b1) is an aulfonated hydrocarbon, optionally in ealt form, and the oil in the oily dispersion is an oil (cg), i.e. a water-immiscible hydrocarbon oil, in which the polymer (a) is not soluble, but is finely divided therein with the water, and optionally adds component f) together with b1) and / or adds bi) as a solution in oil c3); or Ä B) for the preparation of preparations which, as a), a1) contain cationic polymers of vinyl-like monomers, which for the formation of the cationic polymers ai) polymerize the required monomers in the presence of anionic surfactants in the W / O emulsion and optionally distills off water and / or oil and optionally adds additional additives a), b), c>, e) and / or f); or r fl process according to variant B), wherein at least a part of the cationic monomers are present as monomer slats according to claim 6; or 0.1 for the preparation of preparations which, as a), qi) contain copolymer risates of cationic and non-ionic vinyl monomers, prepolymerize the non-ionic monomers, or a part thereof, according to the invested emulsion polymerization process in the presence of c), d) and e) and finally polymerizes after the addition of cationic monomers and optionally the remaining part of non-genogenic monomers in the presence of b), wherein b) is added before, after or together with the cationic monomers and / or in the form of monomer salts, wherein the surfactant anion is the counterion of the monomer cation. In the process according to claim 6 or 7 an intermediate product constituting a W / O emulsion, characterized in that it contains a vinyl-like monomer salt, wherein the cation is a vinyl-like cationic monomer and the anion an anionic surfactant, optionally together with emulsifier 6) constituting a lipophilic resp. oil-soluble, non-ionic surfactant, the oil being a water-immiscible oil in which the polymer is insoluble but finely divided. 9. An intermediate according to claim 8, characterized in that the anionic active substance is an aulfonated hydrocarbon. The use of a preparation according to any one of claims 1-5, as a flocculant, especially for the production of paper and / or for waste water.