NL8300326A - POLYMERIZATE AND SURFACTIVE SUBSTANCE CONTAINING PREPARATIONS AND PREPARATION AND USE THEREOF. - Google Patents

Description

ν_3Γ 4f '• Λ

Polymerisate and surfactant-containing preparations and their preparation and use.

Hydrophilic, that is, water-soluble or dispersible, cationic polymerisates are increasingly used in the art, for example v as a flocculant, and it is of great importance that preparations containing such polymerisations are quickly divisible or diluable with water. It has been found that preparations can be prepared which contain, in addition to excess cationic water-soluble polymerisate, an aniogenic surfactant, optionally in salt-bonded form, the polymerisates in the composition being finely divided and the compositions can be spread well in water or be 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.

A first subject of the invention are thus water-dilutable polymerisate and surfactant-containing compositions, characterized in that they contain a) a hydrophilic, cationic polymerisate and b) an anionic surfactant, the molar proportion of anionic surfactant b) does not exceed the molar content of cationic monomer units of polymerisate a) and wherein the cation of the polymerisate and the anion of the anionic surfactant may be combined with salting.

The hydrophilic polymerisates a) are cationic, that is to say they are free of anionic monomer components, or can be obtained by polymerization of only cationic and optionally nonionic monomers.

Suitable hydrophilic, cationic polymerisates a) are random cationic, addition and condensation polymerisates, for example from the polyamidine, 1Q polyathyleneimine and / or polyetheramine series, such as, for example, in U.S. Pat. Nos. 3,210,308, 3,275,588, 3,329. 657, 3,753,931 and 4,056,510 and in French patent 1,583,363 and / or preferably homo and copolymerisates of vinyl-like cationic and optionally non-ionic monomers. By cationic polymerisates or cationic monomers, in general, we mean here both such products which already contain cationic ones and such products in which the cation is first formed in the presence of water and / or acid, but which are free of anionic monomers to be.

The polymerisations a) occurring in the compositions of the invention are preferably at least in part a ^) cationic homo- and / or copolymers of vinyl-like cationic and optionally nonionic monomers, the polymerisations a) advantageously consisting mainly of a ^). The content a ^) in a) is preferably at least 7.0 wt%, in particular at least 90 wt%, most preferably a) consists exclusively of a ^).

Preferred monomers used to prepare a) are vinyl-like water-soluble monomers, mainly from the acrylic and methacrylic acid ester series, the acrylic and methacrylic acid amide series, the vinyl pyridine series, the diallylamine series , the N-vinyl pyrrolidone series, as well as from the vinyl ether series.

35 Representatives of the above mono- 8300326 - 3 - s * r— i 4.

. . . ..... - - - - -> I --------- ... ...... ...... Μ .-—. Preferred lake classes are of the cationic types of acrylic acid dialkylamine alkyl esters, acrylic acid trialkyl ammonium alkyl esters, methacrylic acid dialkylamino alkyl esters, methacrylic acid trialkylamonium alkyl dihydroxy, acrylic acid dialers acrylzuurtrialkylammoniumhydroxyalkyl- esters, methacrylzuurdialkylaminohydroxyalkylesters, methacrylic acid esters trialkylammoniurohydroxyalkyles, 2- and 4-vinyIpyridine and the corresponding N-alkylpyridiniumderivaten, N-alkyl di-allylamine and the corresponding N-dialkyldiallylammoniumderi-10 barrels, acrylzuurdialkylaminoalkylandden, acrylzuurtrialkyl- ammoniumalkylamiden, methacrylzuurdialkylaminoalkylamiden, methacrylzuurtrialkylammoniumalkylamiden, acrylzuurdialkyl- sulfonium alkyl esters and methacrylic acid dialkylsulfonium alkyl esters The alkylene backbones (namely between N and 0, between 0 and - 15 S and between N and K) advantageously contain 2 to 4, preferably 2 to 3, carbon atoms, the alkyl groups (namely the substituents on the basic nitrogen or sulfur) advantageously contain 1 to 4, preferably 1 to 2, carbon atoms and may optionally be substituted with phenyl and if they are substituted with 20 phenyl then mainly benzyl is suitable, but preferably the alkyl radicals are unsubstituted.

Of the cationic monomers mentioned, the compounds of formulas 1 to 12 are particularly preferred.

25 In these formulas

R 1 hydrogen or methyl, R 2 methyl or ethyl, methyl or ethyl, R 2 hydrogen, methyl or ethyl, 30 A a counterion to the ammonium group and n 2 or 3 for.

The symbol A generally stands for any anion, as is customary with ammonium compounds, preferably a halide ion (in particular chloro-8300326

»V

4-ride, bromide or iodide) or an R 2 SO 4 ion. The symbols and R ^ are shown. preferably each for methyl and the symbol R 'also preferably stands for methyl. In a particular embodiment of the invention, however, A stands for (A ^), that is to say the anion of an anionic, preferably lipophilic, preferably oil-soluble surfactant as further defined below. .

Of the cationic monomer units, the acrylic and methacrylic acid derivatives are generally preferred, especially the optionally quaternized acrylic acid or methacrylic acid dialkylaminoalkyl esters and dialkylaminoalkyl amides or the listed monomer compounds which are of the formulas 1 to 6, respectively. especially formulas 1, 2, 5 and 6 are preferred. Particularly preferred cationic monomers are those of formulas 1 and 2.

Preferred representatives of said classes of nonionic monomers are those of formulas 13 to 16, wherein 20 represents methyl or ethyl and R. j has the above meaning.

Of the nonionic monomers mentioned, the compounds of the formula 13 are particularly preferred, that is to say methacrylamide and in particular acrylamide.

Preferred polymers a) are copolymers from cationic monomers of the formula 1 and / or 2 and nonionic monomers of the formula 13.

The polymerisates a), in particular aj) to be used according to the invention are cationic, that is to say at least part of the corresponding monomers are cationic monomers and the optional others are non-ionic. The content of cationic monomer units is advantageous. 5-100. mole%. preferably 10-80 mol%, especially 10-40 mol% ,. To obtain certain effects and to set certain cation contents, 8300326%. parts of two polymerisates of different cation content, that is to say operate from a weaker cationic and stronger cationic polymerizate and cut them together as desired. Suitable weaker cationic polymerisates are those whose content of cationic monomer units is advantageously from 5 to 20 mol%, suitable stronger cationic polymerisates are those whose content of cationic monomer units is advantageously from 20 to 80 mol%, preferably 30 to 60 mol%.

v

The average molecular weight (average by weight) of the polymerisates can be arbitrarily high, for example, up to 20,000,000 and advantageously they have an average molecular weight of> 100,000, preferably of ~> 500,000, most preferably of> 1,000,000.

As components b), ie as anionic surfactants, generally arbitrary conventional surfactants are included which contain at least one lipophilic hydrocarbon radical and at least one hydrophilic anionic group, such as, for example, in "Surfactant Science Series" ( M. Dekker Ine.,

New York and Basel), vol. 7: "Anionic Surfaetans" (edited by Warner M. Linfield, 1976) - parts 1 and 2 - have been described.

The lipophilic moiety is preferably araliphatic or aliphatic and advantageously contains at least 9 carbon atoms, preferably 12-36 carbon atoms. The anionic group can be any conventional acid group, optionally in salt form, mainly carboxylate, phosphate, phosphonate, sulfate and sulfonate, of which carboxylate, phosphate, sulfate and sulfonate are preferred, but especially a sulfonate group. Optionally, polyalkylene glycol ether groups may also be present in the molecule of the anionic surfactant, but the surfactants preferably do not contain polyalkylene glycol ether groups. Some noteworthy classes of 35 anionic surfactants include the following: 8300326 “6 ~ V” Sulphated fatty acid mono-, di- and tri-glycerides (especially sulphated, natural fats or oils and sulphated monoglycerides), sulphate fatty alcohols and sulfated fatty acid alkanolamides.

Sulphonated hydrocarbons, mainly alkyl sulphonates, olefin sulphonates and alkyl aryl sulphonates, in particular petroleum sulphonates, sulphonated aliphatic carboxylic acids and carboxylic acid esters, especially tf sulphomono carboxylic acids and sulphonomonocarboxylic acid esters and sulphosuccinic acid esters.

*

Partial phosphoric acid alkyl esters.

Aliphatic carboxylic acids (soaps) and carboxy methylation products of fatty alcohols, monoglycerides and fatty acid alkanolamides.

Of the aforementioned anionic surfactants, the sulfonates are particularly preferred, especially petroleum sulfonates.

The anionic surfactants are advantageously at least partly in salt form, with the usual salt cations being suitable for the formation of salt, for instance alkali ions (lithium, sodium, potassium), ammonium ions / both unsubstituted ammonium and substituted ammonium, for example mono, di and tri- (C 1-4 alkyl) ammonium and mono-, di- and tri- (C 1-6 alkanol) ammonium, in particular mono-, di- and triethylammonium, mono-, di- and tri- isopropanol ammonium and mono-, di- and triethanol ammonium /, alkaline earth ions (magnesium, calcium, strontium and barium) and 2 * 3 · 3ί * other polyvalent cations, in particular Zn, Al and 4+

Zr. The anionic surfactants are preferably in the form of the corresponding salts of polyvalent inorganic cations, with calcium being particularly preferred.

The anionic surfactants can have a more or less pronounced solubility or dispersibility in water or can be practically insoluble in water (ie they do not give a true concentration in the concentration used). - solution in water, but can still be dispersible in water and / or preferably be dispersible or soluble in oil, which depends essentially on the choice of the lipophilic residue and on the choice of the cation.

The lipophilic anionic surfactants are preferred, especially when they are soluble in oil in the form of the sodium salt, especially those present in the form of salts of such cations (preferably polyvalent anionic cations) such that they do not give real solutions and give W / O emulsions with water and with corresponding oils, in particular as defined under c), i.e. they have W / O emulsifier character, respectively they are W / O emulsifiers. The above-mentioned anionic surfactants are generally known or can be prepared in known ways. The amine salts and the salts of polyvalent inorganic cations of the anionic surfactants are advantageously prepared in situ, for example, it being favorable to react the alkali salts of these surfactants with water-soluble salts of the corresponding amines and of the polyvalent inorganic cations. In principle, salts of strong inorganic acids (depending on the cation advantageously sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid) and of simple organic carboxylic acids (C 1-4 carboxylic acids, mainly formic acid and acetic acid) are suitable as water-soluble salts, of which the amine salts the sulphates, chlorides and acetates are preferred and of the salts of the polyvalent inorganic cations the formates and especially the chlorides are preferred. Calcium chloride is particularly preferably used.

When the polymerisates contain cationic monomer units, the counterion of which is a surface active anion, their share in the polymer molecule is 8300326

v V

- a - advantageous on average not more than 15 mol%, preferably not more than 10 mol%.

Generally, the polymerisates in the compositions of the invention contain cationic monomer units and optionally nonionic monomer units, with some of the cationic monomer units containing the anion of the anionic surfactant as a counterion to the cation. Schematically, the polymerisates containing the following recurring monomer units can be represented by formulas 27, 28, and optionally 29, where formulas 27 and 28 represent cationic monomer units, ie, recurring cationic units derived from cationic monomers formula 29, i.e., -G-nonionic-15 gene monomer units, i.e., recurring, nonionic units derived from nonionic monomers, Q denotes the portion of the monomer unit that participates in the soil skeleton, and Kat represents the cationic moiety bonded thereto and (Aj) represents a surface active and (A2) represents a non-surface active anion.

Preferred monomer units of formulas 27 and 28 have formulas 27a and 28a, respectively, with formulas 27a and 28a and (Kat +) preferably being residues such that they correspond to the derivatives of formulas 2, 4, 6, 8, 11 and 12. is preferably the anion of any of the above surfactants, advantageously of a lipophilic surfactant (as defined above), in particular one of said sulfonates. A2 preferably represents one of the above-mentioned, non-surface-active anions, such as those which arise, for example, by quateration or protonation, preferably halide or K 2 O-SO 2.

Preferably, the groups of the formula "8300326 i-v-9" and 27a, respectively, have the formula 27b or 27c., In which Aa 'is the anion of. a. petroleum sulfonate, especially of a lipophilic petroleum sulfonate.

Preferred monomer units of formulas 28 and 28a, respectively, have formulas 28b and 28c, where Aa = chloride or R 2 O-SO 2.

Preferred monomer units of the formula 29 correspond to the derivatives of the monomers of the formulas 13 to 16, in particular the groups of the formula 29a, in particular to the formula 29b.

Preference is given to the polymerisates which comprise and consist of the units of the formulas 27a, 28a and 29a, in particular which contain and consist of the units of the formulas 27b, 28b and 29b, respectively.

Advantageously, the preparations also contain: c) an oil immiscible oil, which is insoluble in the polymerisate, but is finely divided therein.

Particularly in this case, it is advantageous that the anionic surfactant b) bf) is a lipophilic, preferably oil-soluble, anionic surfactant.

Component c) can be either a single oil or a mixture of different oils. Generally, arbitrary oils are suitable, for example, such as are used to prepare water-soluble polymerisates containing emulsions and / or dispersions, both natural and synthetic oils. Natural oils include both petroleum refining oils and vegetable and animal oils (triglycerides in principle), and synthetic oils include both synthetic hydrocarbons and modified oils. 8300326 - 10 · -

«► -V

alkanes (hydrocarbons) and fatty acid esters (mainly triglycerides and monoesters).

Some preferred categories of oils are the following: 5 1.: -: Hydrocarbons 1.1 Hydrocarbons from the petroleum refinement, mainly 1.1.1 special gasolines, which are distilled from crude gasoline (boiling range 65-140) ° C) (dearomatized as well as aromatics-containing types) 1.1.2 light gasolines, test gasolines and lacquer gasolines (boiling range 100-310 ° C, preferably 14Q-300 ° C), in particular

aromatics-free cooking range 100-270 ° C

preferably·. 140-250 ° C

Fraction with an aromatic content between

12 and 19% 160-210 ° G

Eractions with an aromatic content between

24 and 45% 140-310 ° C

Eractions with an aromatics content of 80-

90% 160-260 ° C

Purely aromatic

lacquer gasolines 160-310 ° C

1.1.3.Aromate-free hydrocarbons with iso-30 alkane structure (boiling range 110-260 ° C) 1.1.4 Earaffine oils (mineral oils), for example diesel oil, spindle oil, machine oil, cylinder oil, lubricating oil and petrolatum oil.

35 1.1.5 Eating roll date (petrolate) 8300326 * * ».

- 11 - 1,2 »Synthetic hydrocarbons» mainly from the Fischer-Tropsch synthesis or high-pressure carbon hydrogenation, in particular synthetic gasoline

65-170 ° C

Kogasine I 190-230 ° C

Kogasine II 23Ö-330 ° C

Synthetic paraffin

10 oil 300-450eC

1.3. Optionally alkyl-substituted benzenes, mainly benzene, xylene, toluene, methyl ethyl and trimethyl benzenes, dimethyl ethyl and tetra-methyl benzenes, as well as higher alkyl benzenes (C 1 -C 2 alkylbenzenes).

2. Natural vegetable or animal triglycerides, in particular olive oil, peanut oil, cotton oil, coconut fat, rapeseed oil, sunflower oil, corn germ oil, castor oil and claw oil.

3. Fatty acid monoesters, mainly C 1-4 alkyl esters of 2-24 ”*, preferably C 1-2 fatty acids, in particular methyl, butyl and isopropyl esters of stearic, oleic, palmitic, myristic and mixtures thereof.

The petrolates are advantageously consumed in admixture with oils which are liquid at room temperature (200 ° C).

Of the mentioned oils, the most 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 in particular 35 aromatic and low-aromatic varnishes, isoalkanic oils 8300326 - 12 - (1-.1.-3) and mineral .oils. (1-, 1.-4).

. -A special aspect vait. the invention is that c) a mixture of. at least two oils, in particular a mixture of an oil (c) and an oil (c), which are selected such that the O / W-EHLB value of oil c) is greater then the O / W-EHLB value of the mixture of the oils c ^) + c ^). O / W-EHLB value means the optimal HLB value of a hypothetical surfactant required for this oil or oil mixture so that a stable oil-in-water emulsion can be formed. (See, for example, "Cosmetics, Science and

Technology ", Verlag John Wiley and Sons (2nd edition, vol. 3, 1974), pp. 602-607, or Philip Sherman" Emulsion Science ", Academy Press, London and New York, 1968, pp. 146-147, or Paul Becher "Emulsion, Theory and Practice", 2nd Edition, 1965, 15 American Chemical Society, Monograph Series No. 162.

Preferably, the O / W-EHLB value of oil c ^) is less than that of oil c ^).

. Oils c ^) preferably have a 0 / W-EHLB value of 10 to 15. Such oils are among the above mentioned, in particular among those mentioned in sections 1.1.1, 1.1.2, 1.1.3 and 1.3 named. Oils c ^) preferably have an O / W-EHLB value of 7 to 10. Such oils are among those listed above, especially those listed in Sections 1.1.4, 1.1.5, 2 and 3.

In addition to surfactant b), the compositions of the invention may also contain nonionic surfactants. It is expedient if these are lipophilic.

Advantageously, the compositions of the invention also contain d) a lipophilic, preferably oil-soluble, nonionic surfactant.

This component d) may be a single surfactant or a mixture of lipophilic or oil-soluble nonionic surfactants.

8300326 S i »- 13 -

Advantageously, component d) is a W / ö (water-in-oil) emulsifier, i.e. a surfactant which can form a W / O emulsion with at least part of oil c) in the presence of water.

The nonionic surfactants d) are preferably insoluble in water or water only dispersible and advantageously exhibit an HLB value of 8, preferably between 3 and 8, and more preferably between 4 and 7, as W / O emulsifiers. .

When d) is a mixture of nonionic lipophilic surfactants, the individual components of this mixture d) may also have respective HLB values, but are used in such proportions that the mean HLB value of this higher -15 surface-active substance mixture is advantageous ^ 8 and preferably lies between 3 and 8, in particular between 4 and 7.

Component d), that is, as lipophilic, preferably oil-soluble, nonionic surfactant, generally suitable compounds are suitable and essentially compounds which have at least one lipophilic hydrocarbon residue, advantageously with at least 9, preferably containing 9-24 carbon atoms and at least one nonionic hydrophilic moiety which is advantageously an optionally containing propylene glycol units containing mono- or polyethylene glycol moiety and / or the moiety of a higher polyol (eg glycerol, mannite or sorbite). These lipophilic or oil-soluble surfactants may also be referred to as hydrophobic surfactants, and up to the hydrophobic surfactants may also be referred to the hydrophobic Pluronictypes and Tetronics, in which the high polypropylene glycol content may be referred to as a lipophilic moiety. In particular, the following categories of nonionic surfactants can be mentioned:

Mono- or polyoxyethylation and / or oxy-35 propylation products of saturated and / or unsaturated straight 8300326-14 and / or branched aliphatic alcohols, of alkylphols, of.

. fatty acids, of fatty acid alkanolamides, of partial fatty acid polyesters and of vegetable or animal fats or oils and the corresponding etherification and / or esterification products of mono-and / or polyethylene and / or propylene glycols.

Partial fatty acid polyol esters.

Nonionic ethylene oxide / propylene oxide copolymers with a high content of propylene oxide units (Pluronic types) and ethylene oxide / propylene oxide addition products to ethylene diamine with a high content of propylene oxide units (Tetronic types), which are considered non-ionic substances because of the high content of propylene oxide units considered.

The said partial polyol esters are advantageously di- or preferably mono-esters of aliphatic polyols with 3 or more hydroxyl groups, mainly of glycerol, mannite or sorbite.

Preferred nonionic surfactants are generally mono- and / or polyoxyethylation products of aliphatic alcohols, of alkylphenols and of aliphatic fatty acids, partial polyol esters of aliphatic fatty acids, mono- and / or diethers of mono- and / or polyethylene glycols with aliphatic alcohols and / or alkyl-25 'phenols, and mono- and / or diesters of mono- and / or polyethylene glycols with aliphatic fatty acids.

The occurring fatty acid residues can generally be acyl residues of conventional alkyl carboxylic acids or alkenyl carboxylic acids, the alkenyl carboxylic acids being suitable mono-olefinically unsaturated acids.

The alkyl radicals are the only lipophilic radicals (if, for example, in formula 17) advantageously contain at least 9 carbon atoms, preferably 9-24 carbon atoms, in particular 9-18 carbon atoms, and can be linear or branched. In the alkylaryl-35 radicals, such as, for example, in the radical of formula 30, 8300326-15-the alkyl radicals advantageously contain 4-12 carbon atoms and. can also be linear or branched. When the lipophilic moiety of the acyl moieties is carboxylic acid, it is advantageously a fatty acid moiety, in principle, of an alkyl or alkenyl carboxylic acid, which advantageously contains from 9 to 24, preferably from 12 to 20, carbon atoms, with lauric acid, myristic acid, stearic acid and oleic acid are particularly preferred. The polyethylene glycol derivatives, in particular those of formulas 17 and 18, are generally medium formulas, ie formulas in which the indicated number of ethylene oxide units is an average number.

Of the said nonionic surfactants, the compounds of formulas 17 and 18 are particularly preferred.

15 In these formulas

Rg C 24 -alkyl or -alkenyl or a radical of the formula 30, R 1 -CQ- each an acyl radical of an alkyl or alkenyl carboxylic acid with 12-22 carbon atoms, 20 Rg C 4-12 alkyl, X the q-valent residue of glycerol or sor beet or a mono- or polyethylene glycol of the formula 19, p 1 to 6, q 1 or 2, or for sorbite also 3, 25 r 1 or 2 and s 1 to .10 for, the number and length of the lipophilic residues and the number of -CH2-CH2-O groups is expediently chosen so that the HLE value of the nonionic enamel agent or the nonionic emulsifier mixture is between 3 and 8, preferably between 4 and 7.

Especially preferred are the compounds of formulas 20 to 23, in which formulas

Rg Cg-lgalkyl or -alkenyl, 35 R ^ q-CO- an acyl residue of an aliphatic 8300326 ”16 - C12-18 ~ fatty acid * Y- a monovalent residue of sorbite, glycerol or di- or tetraethylene glycol, t 2 to 3.5 k 3 to 5.

and m represents 4 to 9.

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

When c) is a mixture of oils c ^) and c. ^) 15, it is advantageous to choose the surfactants d) and the oils such that the O / W-EHLB of the mixture c ^) + c ^) is as close as possible to the HLB value of d), but advantageously is not smaller than this.

Advantageously, the compositions of the invention also contain e) water.

The polymerisates a) or the polymer salts thereof, which contain the anion of the anionic surfactant as counterion, are hydrophilic, ie they can absorb water or form a gel or sol in the presence of water, or be at least colloidal soluble in water . The relative amount of water used with the oil (c) and with the emulsifier (d) is generally chosen such that the polymerisate is finely dispersed together with the water in the oil (or as a suspension of the polymerisate with water or the water-swollen polymerisate or the aqueous polymer gel in oil, or as an emulsion of the aqueous polymer sol or the aqueous polymer solution in oil).

A particular subject of the invention 8300326

* I

It is also that the compositions additionally contain "f) an oil-miscible, water-insoluble and not self-dispersible polar solvent, which in itself does not exhibit emulsifier properties, but which decreases the water / oil interface tension.

These solvents are generally polar compounds which exhibit an extra low HLB value, but which are still sufficiently polar to collect at the oil / water interface. Advantageously these are water-soluble, aliphatic alcohols or phosphoric acid triesters or Pluronics. The alcohols advantageously contain 5-10 carbon atoms per hydroxyl group, the following in particular may be mentioned: methyl isobutylcarbinol, 2-ethylhexanol, isononanol, isodecanol and 2,4,7,9-tetramethyl-5-decyn-4,7- diol. Of the phosphoric acid triesters, particular mention may be made of tributyl phosphate, triisobutyl phosphate and tri (butoxyethyl) phosphate. Of the Pluronics, Pluronic L101 can be mentioned in particular.

A further object of the invention is a method for preparing the compositions of the invention, characterized in that the anionic surfactant b) is used before, during and / or after the polymerization with the polymerisate a) or with the combines corresponding monomers, wherein the polymerisate or the corresponding monomers are preferably present in as fine a form as possible.

In the case of polymerisates of non-vinyl-like monomers, it is preferable to use the anionic surfactant on the polymerisate, which is present in as finely divided form (for example as an aqueous solution and / or as an oil dispersion, preferably as W / O emulsion of the polymer solution in water). In the case of polymerisations of vinyl-like monomers, it is advantageous if the polymerization takes place in a W / O emulsion and that at least part of the 8300326-18 anionic surfactant is added before the polymerization * and / or before addition of the cationic monomer. attached.

A particular subject of the invention is a process for the preparation of compositions of the invention which contain polymerisates (a), characterized in that the monomers required to form the polymerisates (a) are present in W / O in the presence of anionic surfactants. emulsion polymerizes and optionally distills off water and / or oil and optionally adds further additives a), b), c), d), e) and / or f).

The vinyl-like monomers advantageously take the form of an aqueous solution in the presence of the anionic surfactant and preferably also in the presence of the nonionic oil-soluble surfactant b) in at least a portion of the oil c) emulsified, wherein the water-soluble monomers and in particular the cationic monomers are present in a molar excess with respect to the anionic surfactants. The oil-emulsified water phase also contains further additives, such as, for example, conventional complexing agents, salts and acids and / or bases for adjusting the pH.

In a preferred embodiment of the process, the vinyl-like monomers to be polymerized are introduced into the present W / 0-25 emulsion, which already contains anionic surfactant and optionally non-ionic surfactant and / or further customary additives, or the vinyl-like monomers to be polymerized. in the aqueous dispersion (suspension and / or emulsion) or solution of the anionic surfactant, after which oil and optionally nonionic surfactant and / or further conventional additives can be added, whereby dispersions of the aqueous monomer phase in oil can be prepared. Due to the presence of the anionic surfactant in the monomer containing the W / O emulsion, the cationic monomers - or part of them 8300326 - 19 - can, in particular, under neutral to acidic conditions, in the form of sparingly water-soluble, lipophilic salts of the surfactant are present in which the anion of the anionic surfactant acts as a counter ion to the cationic monomers, and a further subject of the invention are these salts of cationic vinyl-like monomers wherein the counter ion ( A ^) is the anion of an anionic surfactant, preferably a lipophilic or oil-soluble anionic surfactant. These substances preferably have the formula 24.

Preferred salts of the invention have a cation as in formulas 2, 4, 6, 8, 11 and 12 and particularly preferred salts of the invention are formulas 2, 4 and 6, wherein the counterions - 15 originate from said anionic surfactant Aj, in particular from the hydrocarbon sulfonates, in particular from petroleum sulfonates.

Preferred monomer salts of the invention are of formula 25, and in particular of formula 26.

The monomer salts of the invention are preferably prepared by treating an excess of cationic monomers, which do not contain a surfactant counterion, with anionic surfactants, in particular as described above. A particular aspect of this subject of the invention is the very serious W / O emulsions containing these monomer salts.

A special embodiment of the preparation method for the present polymerisate-containing preparations is that an oil dispersion comprising a hydrophilic, cationic polymerisate (a), water (e) and a lipophilic or oil-soluble, non-ionic surfactant (d) but does not contain an anionic surfactant, treating a lipophilic, preferably oil-soluble, water-insoluble, anionic surfactant 8300326-20 (b ^), wherein (b ^) is a sulfonated hydrocarbon, optionally in sun form and the oil of the dispersion in oil is an oil (c ^), that is, a water immiscible hydrocarbon oil, in which the polymerisate (a) 5 is not soluble, but is finely divided therein with the water.

The polymerisates (a) here are preferably vinyl-like polymers (a) as described above. Suitable hydrocarbon oils (e3) are generally oils as described in section 1.1, with those of sections 1.1.1 to 1.1.4, in particular of 1.1.3 and 1.1.4, and especially varnish gasolines being preferred.

The oil dispersions containing (in addition to (e), (ς0) and (d) but not (b) become advantageous by emulsion polymerization of corresponding aqueous monomer solutions in the oil and in the presence of the emulsifier (d) and optionally partial distillation prepared from water.

The polymerization can be carried out in a manner known per se (see, for example, "High Polymers", vol. 9, 1955 "Emulsion Polymerisation", Verlag: Interscience 20 Publishers Inc., New York) and the aqueous system can be used in addition to the inventive required constituents, contain conventional additives, such as, for example, polymerization initiators (preferably compounds which form free radicals under thermal decomposition or a redox system), complexing agents (eg NaEDTA), acids and / or bases for adjusting pH and / or metal salts , for example Na -2+ and / or Ca salts. After inertization (i.e., after expelling the oxygen with inert gas) and after addition of appropriate polymerization initiators, the polymerization takes place. After emulsion polymerization has taken place, for example after

the combination of anionic surfactants and cationic polymers, especially after diluting with water, cationic groups in corresponding salt form may also be present in the polymerizate. Polymerization is normally exothermic and occurs, for example, at a pH

8300326 - 21 - between 2 and 8, advantageously under acidic conditions, preferably at a pH 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 wt.%, Preferably 30-65 wt.% (Based on the total emulsion). The polymerization can be carried out adiabatically or isothermally, but it is preferably carried out partly adiabatically, ie with a limited rise in temperature by dosed addition of the initiator and / or by cooling of the reaction mixture, advantageously at values of ≤ 120 ° C. , possibly under pressure. It is preferred to operate between 30 and 110 ° C. If the mixture to be polymerized contains hydrolyzable monomers (in particular esters or primary amides), effective reaction conditions are chosen such that hydrolysis to the undesired acids is avoided as much as possible.

With the surfactants to be used according to the invention, very finely divided dispersions can also be obtained with relatively little surfactant. By the emulsion polymerization, very high molecular weights of the polymerisates can be achieved, so that a very wide spectrum of molecular weights of the polymerisates can be available, which also allows a very wide range of application of the compositions of the invention.

The emulsion polymerization is expediently carried out in the presence of at least part of the oil c).

For the emulsion polymerization, advantageous oils are used, in which at least a part, preferably at least 50 wt.%, In particular preferably at least 80 wt.%, Are hydrocarbons, with aliphatic hydrocarbons being preferred as much as possible. The relative amounts of water and oil, as well as the concentration of the monomer solution in water, can vary widely, the economy being preferably as concentrated as possible. The W / O emulsion to be polymerized contains at least a part of the surfactant b) (preferably b ')) and / or to the extent necessary to obtain a sufficiently stable W / O emulsion for the polymerization. . After the polymerization has taken place, the resulting polymer-containing W / O emulsion can be treated with further additives, for example with further components a), b), c), d) and / or e) 5 and / or with component f) - and / or and can reduce the content of components c) and / or e), for example, by distillation.

These additional modulations of the polymerisate-containing W / O emulsions can, in particular, improve the properties of the compositions, for example their stability and / or their dilutability with water. If the preparation is to contain other polymerisates a) in addition to polymerisate a ^), the latter are preferably added after emulsion polymerization has taken place.

If the preparation still has to contain component f), it is advantageously added to the preparation last or after emulsion polymerization has taken place. It is advantageous to use f) in dilute form with little oil c), but if desired larger quantities of oil c) can also be used and / or further additives a can be added together with f) or its solution in oil c) ), b), d) and / or. optionally e) added to the preparation.

If the preparation is to contain a mixture of oil and c ^) and c ^), the emulsion polymerization is advantageously carried out in oil e.j), which optionally contains c ^). Oil c ^) and any residual oil c ^), if necessary, can be added after emulsion polymerization has taken place, optionally after distilling off the water or most of the water, respectively.

The preferred mixture composition of the compositions of the invention and the above-described compositions should be schematically represented as follows: the composition contains per 100 parts by weight of component a) 35 x parts by weight of component b) 8300326 - 23 - y parts by weight 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 the concentrations required for the aqueous monomer-containing dispersion to remain sufficiently stable during the polymerization. X Advantageously amounts to at least 0.5, mainly 1-30, preferably 1.0 -15, in particular 1.5-10 10. The above-mentioned mixing ratios of a) and b) relate to the respective components without taking into account a corresponding salt formation in the numbers 100 for a) and x for b), but must also include the possible salt formation of a) + b), z is advantageously 0-80, preferably 1-80 and most preferably 2-30. It is advantageous if the compositions of the invention contain oil and y is preferably 30-400, most preferably 40-200. The water content can fluctuate widely and is partly also dependent on the oil content, ie on y, insofar as the compositions of the invention in the oil-undiluted form, if they contain water, which contain predominantly in the discontinuous phase, i.e. oil is the continuous phase and the water phase is dispersed or emulsified therein.

After the (inverse) emulsion polymerization, the water, preferably azeotrope, can be distilled off, theoretically all the water can be distilled off, that is to say u 0, which is however not preferable in practice, because the residual water is difficult , which causes the polymerizate to swell, to be distilled off completely. On the other hand, water can optionally be added to the W / O emulsion containing polymerisate 30, for example also in the form of another W / O emulsion or an aqueous solution of a polymerizate a), so that the water content of the preparation also can be relatively high. u Affordably amounts to 0-300, preferably 1-300, preferably 2-200. From an economic point of view, it is preferable not to distill all the water and 8300326-24 - the water content u is advantageously from 5 to 300, preferably from 10 to 200.

In order to further facilitate the dispersibility of the polymer in water by dilution, it may be advantageous to the composition; adding component f), wherein component f) is used in the smallest possible amounts, in particular in amounts smaller than y (component f) is dissolved in component c)). Advantageously v is 0-30, preferably 0-15.

The compositions of the invention advantageously exhibit the following composition: on 100 parts a) x = 1-30 y = 30-400 z = 1-80 h = 0-300 v = 0-30, (where v ^).

A particularly preferred composition of the compositions of the invention is the following: in 100 parts a) 20 x = xT - 1.5-10 y = y '= 40-200 z = z' = 2-30 u = u '- 2 -200 v = v '- 0-15 and v' <25 The oil-containing preparations of the invention are dispersions which can exhibit very distinct viscosities and very thin liquid preparations can also be prepared. Thus, the viscosity (Brookfield rotational viscosity, measured in LV viscosimeter) of the dispersions 30 may be, for example, between 5 cp (axis number 2) and 10,000 cp (axis number 4), preferably between 50 cp (axis number 2) and 5,000 (axis number 4). The dispersions of the invention are also stable, ie they can be stored for a long time without change, or, when the dispersions separate into layers, they can be returned to the original by simple stirring. moderately dispersed form. Particular attention should be drawn to the very good water dispersibility and water dilutability of the compositions of the invention, in particular the c) -containing compositions, and they can even be added by simply adding the compositions to water or of water to the preparations are diluted very quickly with stirring, but for predilution with water one can also use the usual diluents which exist in the art and are described in numerous places in the literature . Particularly suitable are diluents operating with water jet pumps, ie the polymer dispersion is pumped through a sprayer and the water is pumped through another sprayer into a "chamber" such that the water entrains the dispersion at high speed, after which the mixture is further distributed in the water in various ways, for instance over drip plates or walls or using high shear forces by pumping in and out in "resting tanks" A particularly valuable method for diluting the dispersions of the The invention with water is characterized in that the dispersion is led through at least 1 sprinkler 1 into a water stream such that the water stream washes over this sprinkler 1, 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 sucked by the water flow in such a way that the adhesion and / or cohesion However, in the dispersion at least in part be conquered, but in principle no shear forces are generated in the flow such that the molecules in the dispersion are thereby reduced, the product-water mixture is then accelerated through a narrowed line and then in a dilated mixing zone. decelerates again, with acceleration and deceleration being carried out so many times until the desired distribution of the product in water is achieved and after the dispersion and water come into contact, the process without using filters or 8300326-26 sieves, is carried out.

It is particularly worth noting a device (mixer) for carrying out this dilution method, which uses a pipe 2 provided with a nozzle t for 5 to supply the viscous product, a pipe 3 for the supply of water, a pipe 4 for the acceleration of mixing, a delay zone 5 and a line 6 for removing the product diluted with water.

If an additive is desired in the water medium for diluting with water, for example a surfactant (in particular an O / W emulsifier), this can advantageously be dosed, for example, in line 3.

The overall device is preferably tubular and divided into chambers. Line 3 for supplying the water is expediently arranged at one end of the device coaxially therewith, and line 2 for the supply of the dispersion is preferably arranged at right angles to line 3 to the device, and preferably so that sprinkler 1 is as close as possible to the mouth of pipe 3 and advantageously such that the spray surface is between boundary and axis of the direct water jet.

The first part of the device, ie the chamber to which lines 2 and 3 are arranged, can also be referred to as a "entrainment chamber", because the viscous product, which comes out of the nozzle, is sucked in by the water jet from 3 or get swept up earlier. Sprinkler 1 can consist of a single opening, for example a round opening or a slit, but it can also be a plate with several holes (advantageously 1 to 20 openings, each with a diameter of 0.2 to 5 mm), which is especially important in the case of strong viscous products are preferred, so that a first distribution of the product already takes place through the nozzle. The water flow on leaving line 3 can be laminar to turbulent, but is preferably turbulent.

The volume flow and the speed of the water are expediently chosen as a function of the product to be diluted, with the greatest possible turbulence and speed of the water being generally preferred in the 8300326-27. The Reynolds number at the exit of tube 3 is advantageously from 10,000 to 100,000, preferably from 25,000 to 75,000.

5 In the second half of the entrainment chamber, in the vicinity of the sealing wall, pipe 4 is provided, which can be a tube or also a hose (simplest a hose, whose internal diameter is smaller than the internal diameter of the entrainment chamber, so that the mixture of water and product therein is accelerated Advantageously, the internal diameter of pipe 4 is not less than half of the internal diameter of pipe 3 and not larger than half of the internal diameter of the entrainment chamber or the mixing chamber Advantageously, the internal diameter of pipe 4 is equal to that of pipe 3 ± 50%. It is particularly preferred that pipes 3 and 4 have the same internal diameter. The internal volume of connecting pipes 4 is advantageously no greater than the internal volume of entrainment chamber R. Preferably the connecting pipes are 4

R R

20 as short as possible (internal volume ^, preferably ^^).

More than one nozzle for pumping the viscous product can also be arranged in the entrainment chamber. For example, when the mixer is installed perpendicularly (for example, when the dilution water is pumped through pipe 3 perpendicularly from top to bottom or from bottom to top in the mixer), for example, several nozzles can be radial about the axis in the vicinity of the outlet of pipe 3 or, in the horizontal arrangement of the mixer, for instance several nozzles can be arranged one behind the other. Horizontal arrangement of the mixer (see figure) is preferred and pumping the dispersion through a single tube 2 is simplest and preferred. After the diluted mixture has accelerated through line 4, it flows into delay zone 5 and into mixing chamber M, respectively, where the mixture is preferably retarded to form vortices. From mixing chamber 8300326 __ 28 __ t *

M, after further acceleration, the mixture exits through line 6 or through another line 4 (with repeated acceleration). The ratio of the internal diameter of pipe 3, pipe 4 and pipe 6 or 7, respectively, to the internal diameter of the (cylindrical) chamber R and M, respectively

is preferably 1: 3 to 1:20.

A schematic representation of such a mixer with horizontal arrangement of the chambers is shown in figure 1. In figures 1.1 and 1.2 the 10 essential components are shown as imaginary fragments, namely in figure 1.1 at the end A of the mixer through tube 3 the water is pumped in and the viscous product is pumped into the connecting part B through tube 2 and sprinkler 1. Part B may be recurring, but preferably B is a single part. In part C, pipe 4 is fitted and part 5 of the drawing represents the deceleration zone. The essential part C may be recurring. Advantageously, part C occurs 1-10 times, preferably 2-6 times. The multiple lines 4 may have the same diameter between themselves or the diameter 20 can vary, for example increase regularly, for example when the viscosity of the diluted product increases with a finer distribution. It is simplest if all common lines 4 are the same. In Figure 1.2, the same device as in Figure 1.1 is shown, except that the layout has been clarified instead of acceleration and deceleration zones in chambers, ie R represents the entrainment chamber, which consists of parts A, B and and M represents a mixing chamber, which may be recurring (such as part C of figure 1.1). The diluted product is withdrawn through line 6 (and line 7 of the last chamber, respectively).

Line 6 (line 7 of the last chamber, respectively) may have the same diameter as lines 4 (respectively, as the last of lines 4) or have a different diameter, for example a somewhat larger diameter (for example up to 50% larger), in this case pipeline still has an acceleration of 8300326 - 29 - the diluted product. A further preferred arrangement of the chambers is given in Figure 2.

The device can be built in different sizes as required. For example, the internal voltime of each individual chamber can vary from a few cm3 to about 1 m3, the corresponding pipes, nozzles and connecting lines having proportional dimensions. The internal volume of chambers R and M may vary up to ± 50% if desired, but preferably the involved chambers are mutually equal in internal volume. The mixing chambers are advantageously built in such a way that they can be mounted or removed as separate elements and can be connected by hoses 4, so that the number of mixing chambers can be varied as required in the same device. It is also expedient if the individual lines 2, 3, 4 and 6 and 7, for example, are arranged, for example, by nozzles, so that they can each be assembled as required or exchanged for another with a different diameter. Sprinkler 1 is also advantageously arranged on the pipe 2 concerned in such a way that it can be exchanged as required, in particular depending on the viscosity of the polymer dispersion.

The mixer of the invention is effectively operated in such a way that it is almost completely filled with liquid and, furthermore, the different liquid flows do not collide with parts or walls of the mixer, but such that they form swirls in the liquid. Depending on the solubility or dispersibility of the product and any swelling effect in water (respectively increase in viscosity), the number of mixing chambers and the diameter of the different pipes and tubes, as well as the initial velocity of the water can be selected and optimized accordingly. A measure of the acceleration and deceleration effect at given Reynolds number of the inflowing water and at given device is the pressure drop between inflowing water and outflowing diluted product. The lowest pressure drop required to achieve a good distribution or dilution can also vary with the product used and is advantageously 0.2 bar. In the case of a medium-sized mixer (internal volume of the mixer in an order of magnitude of 10 to 10 m3), it is preferred to operate in such a way that the pressure difference is not less than 0.5. The upper limit of the pressure difference is determined by the resistivity of the device. Good dilution effects are achieved with a medium-sized mixer at a pressure difference of 55 bar or 2,5 2.5 bar and with good dilutable products even at a pressure difference of 1,5 1.5 bar. Although better dilution effects are achieved at a pressure differential as high as possible (ie a faster fine distribution), it is preferable for constructional reasons and also for economic reasons if the inlet pressure of the water can be kept as low as possible. Good results can be obtained with a medium-sized mixer at a pressure difference of 0.5 to 2.5 bar, especially at a pressure difference of 0.6 to 1.5 bar. The mixer of the invention can be operated very quickly and ready-to-use diluted preparations can be obtained within a few seconds.

Due to the very rapid water dilutability of the compositions of the invention, many continuous industrial scale processes using cationic polymerizers can be carried out very efficiently and at optimal dosing rates. It is also particularly worth noting that the compositions of the invention can exhibit a high concentration of cationic polymerisates, and in addition, the biodegradability of the compositions can be mentioned.

The compositions of the invention are distinguished by their water-dilutability and water-dispersibility, and the invention relates to such compositions at arbitrary concentration, insofar as they are still water-dilutable, or the water-soluble polymerisates or dispersions. Be edible, dissolved or dispersed, respectively.

Particularly meant are highly concentrated preparations, especially those containing at least 10 wt.% Cationic polymerisate, and prediluted preparations, especially those containing at least 0.001 wt.%, Preferably at least 0.1 wt.% Cationic polymerisate.

The compositions of the invention can be used in a variety of technical fields, where cationic water-soluble polymerisates are used. In particular, they can be used as flocculants and a further subject of the invention is the use of the compositions of the invention as flocculants, preferably as paper retention and dewatering agents and as flocculants for aqueous slurries, especially soils swallow and clean sludge from municipal sewage treatment plants. Also subject of the invention is a method for manufacturing paper, characterized in that a preparation according to the invention is used as retention and / or dewatering agent.

In papermaking using the compositions of the invention, particularly homogeneous leaf formation can be observed.

The required concentration of the preparation for the application in question naturally refers to the concentration of active substance (polymerisate) for the flocculation involved.

The mixer described above can be used in any installation in which corresponding products diluted with water have to be dosed continuously.

Particularly suitable are installations in which the diluted, water-soluble or at least water-dispersible high polymers are to be dosed, for example flocculants in the processing or purification of the waste water in papermaking (in particular as retention and / or dewatering agent), in the slurrying of boron-sand and / or other minerals in sand or colloidal form or 8300326-32 - also in the residual oil extraction in the petroleum industry. Due to the rapid fine distribution of the polymerisates according to the present dilution process and with the present device, corresponding dilute solutions or dispersions can be obtained even without having to switch on a residence time or residence vessels and the corresponding mixer of the invention can be directly installation.

A further object of the invention is even the use of the mixer of the invention as a diluent station for the polymer dispersions of the invention in plants in which the corresponding products are to be used as flocculants in dilute form, especially in papermaking plants and foot-water purifiers.

In the following examples parts by weight and parts by weight are percent by weight and the temperatures are in ° C. Unless otherwise specified, the products used are commercially available products.

20

Example I

43.5 parts of emulsifier (B ^) are mixed with 800.0 parts of water to give a very fine opalescent emulsion. Now to form the calcium salt of 25 (B ^) 8.2 parts of calcium chloride is added. Immediately a strong precipitate is observed, which corresponds to the formation of the water-insoluble (oil-soluble) calcium sulphonate. Then, while stirring, 440.0 parts of white spirit (C 4) is added. A water-in-oil emulsion is formed, which is stabilized by the addition of 99 parts of emulsifier (D 4). To this water-in-oil emulsion is then added in the order given, 353.0 parts of 75% methacryloyloxyethyl trimethyl ammonium chloride solution in water, 454.0 parts of acrylamide, 1.4 parts of ethylenediamine tetraacetic acid disodium salt, 0.7 parts of iron (III) sulfate and 0.7 parts of t-butyl hydroperoxide added.

8300326 - 33 -

The pH of the water phase is approximately 3.0. The resulting dispersion is then inertized with nitrogen and heated to 35 ° C. Once this temperature has been reached, an air-freed solution of 2.7 parts of sodium thiosulfate in 50.0 parts of water is started to drop. The addition is effected within 8 hours, the temperature being kept between 35 and 40 ° C by cooling.

After the addition of the sodium thiosulfate solution, the polymerization reaction is ended. A stable fine thin liquid polymerisate-containing dispersion is obtained, which exhibits a viscosity of 1000 cp (Brookfield, axis 3.60 rpm). The product is very dilutable with water: approximately 30-40 seconds after the addition to cold water, the maximum viscosity has already been reached with a 1: 200 (0.5Z) dilution in water. The viscosity of a freshly prepared 1: 100 diluted (= * 1%) preparation in water is approximately 500 cp. (Brookfield, axis 3.60 rpm).

Example II

454.0 parts of acrylamide, 353.0 parts of 75% methacryloyloxyethyltrimethylannonium chloride aqueous solution, 1.4 parts of ethylenediamine tetraacetic acid disodium salt, 0.7 parts of iron (XII) sulfate, and 9.8 parts of calcium chloride are added, with stirring, in the order indicated. to 600.0 parts of water. The resulting solution is then mixed with a solution of 52.0 parts of emulsifier (B ^) and 80.0 parts of emulsifier (D ^) in 600.0 parts of gasoline (G ^). A water-in-oil emulsion with a pH (water phase) of 3.0 is formed, which is then inertized with nitrogen. Then, to initiate the polymerization reaction, first 0.7 parts of t-butyl hydroperoxide and then an air-free solution of 1.1 parts of sodium thiosulfate in 12 parts of water are added. A strong exothermic reaction occurs immediately, the temperature rising from room temperature to 90a in spite of light cooling. A thin liquid, 8300326 - 34 - polymerisate, easy to dilute with water, is obtained. dispersion.

Example III

24 parts of the emulsifier (B ^) are mixed with 480 parts of water to obtain a very fine opalescent emulsion. 564 parts of 75% methacryloyloxyethyl trimethyl ammonium chloride solution in water are added to form the corresponding methacryloyloxyethyl trimethyl ammonium petroleum sulfonate. Then, in the order indicated, with stirring, another 480.30 parts of acrylamide 1.43 parts of ethylenediamine tetraacetic acid disodium salt - 0.77 parts of iron (III) sulfate 480.0 parts of white spirit (C ^) 30.0 parts of emulsifier (D ^) 30.0 parts of emulsifier (D ^) 4.8 parts of calcium chloride 20 0.6 parts of t-butyl hydroperoxide added. The resulting dispersion is then inertized with nitrogen and heated to 30 ° C. Once this temperature has been reached, an air-free solution of 2.97 parts of sodium thiosulfate in 42 parts of water is instilled.

The addition is made within 8 hours, with the temperature rising to 50 ° C. A fine, polymerisate-containing dispersion is obtained, which is easily dilutable with water.

Example IV

500.0 parts of the according to Example I.

The resulting preparation is mixed with 10 parts of white spirit (C ^) and 10 parts of emulsifier (B ^) with stirring. Evacuation is then carried out at 26 mbar and the temperature is raised from room temperature to 40 ° C, with approximately 200 parts of water being regularly distilled off with a water separator. 8300326 35 ~ produces a fine, stable polymerisate-containing dispersion, which is easily dilutable with water.

Example V

The procedure is as described in example I.

and to the resulting preparation, add 10% (calculated on the weight of the preparation obtained according to example I) of the 20% preparation according to example 3.1 of French patent 1,583,363 with stirring, also including a stable W / O emulsion.

Example VI

Part 1: dispersion (1) 454.00 parts of acrylamide, 353.00 parts of 75% methacryloyloxyethyltorimethylammonium chloride solution in water, as well as 800.00 parts of water are placed in a sulfate flask and stirred. After the acrylamide is 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 0.10 parts of 30% sodium hydroxide solution. , 0. Then a solution of 143 parts of emulsifier (D ^) in 440 parts of white spirit (C ^) is allowed to flow into the monomer solution with vigorous stirring.

A milky water-in-oil emulsion forms, which is then evacuated five times to a pressure of 26 mbar and each time left with nitrogen. Subsequently, a strong nitrogen stream is passed through the air-free emulsion at a high stirring speed. 0.67 parts of t-butyl hydroperoxide are then added to the cold reaction mixture and heated to 35 °. Once this temperature has been reached, 50 parts of solution of 2.70 parts of sodium thiosulfate in 50.00 of water is dripped within 5 hours on the monomer emulsion. During the thiosulfate addition, the exothermic polymerization reaction begins, keeping the temperature at 36-38 ° by light cooling. The mixture is then post-reacted for another 2 hours at 35 [deg.] And then cooled to room temperature 8300326. The nitrogen supply is shut off and the product is let out.

Part 2: Addition of (b ^) 5 200 parts of the dispersion (1) prepared according to part 1 are mixed with 20 parts of petrol (C2) as well as with 20 parts of 30% mineral oil solution of the petroleum sulfonate (B ^) in the form of the calcium salt. A thick liquid product is obtained, which, however, despite the high viscosity, can be quickly diluted with water when added to water (for example 4 parts of product to 396 parts of water).

Part 3: Preparation of (b ^) - · The petroleum sulfonate (B ^) in the form of the calcium salt is prepared when treating a 20% aqueous emulsion of (B ^) (sodium salt) with an excess of CaCl 2, the precipitated (B ^) - calcium salt. filter, wash with water and dry under vacuum at 60-70 °.

20

Example Vlij 200 parts of dispersion (1) according to example VI (part 1) are mixed with 25 parts of a solution of 10 parts of alkanesulfonate (B ^) in the form of the calcium salt in 80 parts of white spirit (C ^) and 30 parts of mineral oil (C ^) treated.

The resulting mixture is very easy to dilute with water. The calcium salt of the surfactant (B ^) is prepared in analogy to Example VI, Part 3, using the corresponding amount of (B ^) instead of (Bj).

30

Example VIII

200 parts of the dispersion (1) according to Example VI (part 1) are added with 30 parts of a solution of the following percentage composition: 35 8300326 "37 - 14.3% petroleum sulfonate sodium salt (B2) 57.1% mineral oil (C ^) 28.6% 50% solution of triisobutylphosphate (F ^) in isobutanol 5. A thick liquid preparation is obtained, which can be easily diluted when added to water.

Example IX

2210 parts of the according to example I

After the addition of 330 parts of mineral oil (C ^) and 330 parts of petrolatum (C ^), the prepared polymerisate-containing emulsion is stirred at 26 mbar with stirring and heated to 40 ° C within 6 hours, whereby 860 parts of water are regularly adjusted with a water separator. distilled. Along with the water, a small amount of oil distils which collects in the water separator on the water surface and is regularly recycled back into the reaction vessel. A very fine, stable, slightly thick liquid dispersion is obtained, which can be diluted with water approximately as well as the product of Example I.

20

Example X.

To a nitrogen-inerted dispersion, consisting of 960.0 parts of water 25 816.6 parts of acrylamide 1128.0 parts of 75% methacryloyloxyethyl trimethyl ammonium chloride solution in water 2.9 parts of ethylenediamine tetraacetic acid disodium salt 30 1.5 parts of iron (III) sulfate 9.1 parts of calcium chloride 48.0 parts of emulsifier 60.0 parts of emulsifier 60.0 parts of emulsifier 35 960.0 parts of gasoline (C ^) 8300326 - 38 - which was adjusted to pH 3.0 with little sulfuric acid. To initiate the polymerization reaction, first 1.2 parts of t-butyl hydroperoxide added. Then, an air-freed solution of 6.5 parts of sodium thiosulfate in 20.0 parts of water is added dropwise.

The addition takes place within 8 hours, the temperature rising to approximately 48 ° C despite cooling.

After the thiosulfate addition, 165.7 parts of mineral oil (C ^) as well as 27.7 parts of emulsifier (D ^) are added to the polymerizate-containing emulsion and the mixture is distilled under vacuum (20-26 mbar) and at an internal temperature of at most 50 ° C with a water separator approx. 1186 g of water.

A very fine, thin liquid dispersion is obtained, which is mixed with 157.5 parts of olive oil (5) and 157.5 parts of 2-ethylhexanol (F 2) after distilling off the water. The olive oil and dispersion containing 2-ethylhexanoil can be immediately diluted in water.

Example XI

The procedure is exactly the same as in Example X, but 2-ethylhexanol (F ^) is replaced by triisobutylphosphate (F ^).

Example XII

The procedure is exactly the same as in Example X, but 2-ethylhexanol (F ^) is replaced by tri-butoxyethyl phosphate (F ^)

Example XIII

The procedure is exactly the same as in Example X, but 2-ethylhexanol (F ^) is replaced by 2,4,7,9-tetramethyl-5-decyn-4,7-diol (F ^). 1 8300326 _ 39 "ψ

Example XIV

43.5 parts of emulsifier (B ^) are mixed with 834.0 parts of water to give a very fine opalescent emulsion. Now 8.2 parts of calcium chloride is added to form the calcium salt of 5 (Bj). Then, while stirring, 557.0 parts of acrylamide, 216.0 75% of methacryloxy-oxyethyl trimethyl ammonium chloride solution, 1.4 parts of ethylenediamine tetraacetic acid disodium salt, and 0.7 parts of iron (III) sulfate are added to form a cloudy solution. Now 400.0 parts of isoalkanic solvent (Cg), 40.0 parts of mineral oil (C ^), 100.0 parts of emulsifier (D ^), as well as 13.0 parts of emulsifier (B ^) are added. A water-in-oil emulsion forms, which is inerted with nitrogen. Thereafter, 0.7 parts of t-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 to initiate the polymerization reaction. An exothermic reaction occurs, the temperature rising to 85 ° C despite cooling. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 8 300 326

Example XV

2

As in example XIV, the following 3 changes are used: 4

709.0 parts of water is used instead of 834.0 parts.

6

183.3 parts of acrylamide are used instead of 557.0 parts.

8

714.0 parts of 75% methacryloyl-oxyethyltrimethylammonium chloride solution are used instead of 216.0 10 parts.

11

The temperature rises to 43 ° C under adiapatic conditions.

13

After the polymerization, 33 more parts are added to 14

Pluronic L101 (F5) and 165 parts of fatty acid methyl ester mixture (C ^) 15 were added.

16 - 40 ~

Example XVT

Men. works as in. example XIV with the following changes .:

160.0 parts of mineral oil (5 CCg) is used instead of 40.0 parts of mineral oil (C ^)

The temperature becomes between 35 and 40 ° C

kept.

Example XVII · 10 43.5 parts of emulsifier (B ^) are mixed with 800.0 parts of water to obtain a fine opalescent emulsion. Then, in the order indicated, 8.2 parts of calcium chloride, 363.0 parts of acrylamide, 124.0 parts of diallylamine, 353.0 parts of 75% methacryloyloxyethyl trimethyl ammonium chloride-15 solution, 131.0 parts of hydrochloric acid (34%) to adjust the pH to 3.0, 1.4 parts of ethylenediaminetetraacetic acid disodium salt and 0.7 parts of iron (III) sulfate. A homogeneous monomer solution is formed, to which is then added 400.0 parts of white spirit (C ^), 40.0 parts of mineral oil (C ^) and 100.0 parts of emulsifier (D ^). A fine emulsion forms, which is inertized with nitrogen. Thereafter, 0.7 parts of d-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 to start the polymerization reaction. An exothermic reaction occurs, in which the temperature rises to 65 ° C under adiapatic conditions.

Example XVIII

As in example II, the following changes are used:

Instead of 52.0 parts of emulsifier (B ^), 29.0 parts are now used.

Instead of 80.0 parts of emulsifier (D ^), 49.0 parts of emulsifier (D ^) and 65.0 parts of emulsifier (D.) are now used.

4 8300326 - 41 -

Example XIX

43.5 parts of emulsifier (B ^) are mixed with 800.0 parts of water to form a fine opalescent emulsion. 8.2 parts of calcium chloride and then 454.0 parts of acrylamide, 353.0 parts of 75% methacryl-oyloxyethyl 1 trimethylanmionium chloride aqueous solution, 1.4 parts of ethylenediamine tetraacetic acid disodium salt and 0.7 parts of iron (III) sulfate are now added. The resulting solution is then mixed with 400 parts of petrol (C ^), 40.0 parts of mineral oil (C3), 100.0 parts of emulsifier (D ^) and 54.0 parts of emulsifier (B ^). A water-in-oil emulsion forms which is inertized with nitrogen. Thereafter, 0.7 parts of t-butyl hydroper oxide and then 45.0 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 strong exothermic reaction takes place, the temperature rising to 90 ° C within 90 minutes.

Example XX

43.5 parts of emulsifier (B ^) are mixed with 600.0 parts of water. Now, in the order indicated, 8.2 parts of calcium chloride, 454.0 parts of acrylamide, 1.4 parts of ethylenediamine tetraacetic acid disodium salt, 0.7 parts of iron (III) sulfate, 400.0 parts of white spirit (C1), 40.0 parts mineral oil (C3), 100.0 parts of emulsifier (D ^) and 13.0 parts of emulsifier were added. A water-in-oil emulsion is formed, which is then inerted with nitrogen and with 0.7 parts of t-butylhydroperoxide, as well as with 1.0 part of a solution of 2.7 parts of sodium thiosulfate in 50.0 parts. water treated. An exothermic polymerization reaction immediately takes place, keeping the temperature at about 60 ° C. Shortly before the exothermic reaction has ended, an air-freed solution of 265.0 parts of methacryloyl-ethyl-trimethyl-ammonium chloride in 288.0 parts of water is started to drop, the temperature rising again and cooling at 55-60 ° C. 8300326 - 42 - kept. After the exothermic polymerization reaction, stirring is continued for 1 hour at 55 ° C and cooled to room temperature (20 °).

Example XXI

5 The following changes are used as in example XV:

11.00 parts of emulsifier (B ^) is used instead of 43.50 parts.

25.00 parts of emulsifier (D4) 10 is used instead of 100.00 parts.

3.25 parts of emulsifier (B1) are used instead of 13.00 parts.

After the polymerization, F5 and C7 are not added. - · 15

Example XXII

As in example XVI, the following changes are used:

21.75 parts of emulsifier (B1) 20 is used instead of 43.50 parts.

50.00 parts of emulsifier (D ^) is used instead of 100.00 parts.

6.50 parts of emulsifier (B ^) is used instead of 13.00 parts.

25

Used emulsifiers.

Emulsifier (B ^): 62% solution of a petroleum sulfonate (monosulfonate) in the form of the sodium 30 salt of molecular weight 440-470 in mineral oil.

Emulsifier (B1): 60% solution of a petroleum sulfonate (monosulfonate) in the form of the sodium salt of molecular weight 480 in mineral oil.

35 8 300 326 - 43 -

Emulsifier (B ^): Secondary N-alkane sulfonates prepared by sulfoxidation of - alkanes in the form of the sodium salts, in which the alkane residue gives on average the following composition: 5 C ._- C._ = 58% «K 3»> C17 < 3%

<C13 <1Z

Emulsifier (D ^: ct 2E25 ~~ ^ OCE2CE2 ^ r ° E

HLB = 6.5

Emulsifier (Dj: G ^ gH ^ - (OOCI ^ CH ^ - ^ j-OH HLB * 6.5 15

Emulsifier (D ^): Sorbitan monooleate HLB * 4.0

Emulsifier (D ^): Mixture of ^ E ^ COCOCE ^ - 20 ®2> «, ϊ ° -C ° -Cl7 ^ 3“ ® mole ratio 1: 1 average HLB = 7.0

Used oils 25

Lacquer gasoline (C ^): aromatics-free terpenaline, boiling range 193-247 ° C, average molecular weight 137.

Lacquer gasoline (C 1): low-aromatic terpenaline, -1 / r-30 cooking range 190-250 ° C, average molecular weight 180, aromatics content 0.5%.

Mineral oil (C ^): Partially unsaturated mineral oil with the following specifications: 35 Density 0.85-0.95 f 8300 326 44

aniline point 70-8O ° C

* iodine number 20-30.

Petrolatum (C ^): Petrolatum with solidification point 50-85 ° C and cone penetration at 25 ° C 160-180.

Olive oil (C ^):

Isoalkane (C,): Isoalkanic oil with: ———- β-

1 0 boiling range 210-260 0C

aniline point 88 ° C isoalkane content 80% density 0.78 15 Fatty acid methyl ester mixture (C ^): Methyl esters of C. | 2 to C ^ q fatty acids with the following specif ications: density 0.87-0.90 acid number 1.12 saponification number 190-200 20 iodine number 100-110 hydroxyl number 40-60

Mineral oil (Cp): Hydrocarbon mixture with the following specifications: 25 density 0.85-0.95 aniline point 95 ° C viscosity (20 ° C) 30 cp

Solvents used (f) 30 (F ^) triisobutyl phosphate (50% solution in isobutanol) 2-ethylhexanol (F ^) tributoxyethyl phosphate (F ^) 2,4,7,9-tetramethyl-5-decyn-4,7-diol 35 (F ^) Pluronic L101: ethylene oxide-propylene- 8300326 • 45 oxide copolymer of molecular weight 3610 and 10 wt% ethylene oxide units.

Dilution example I

A mixer is used, in which a entrainment chamber and 5 mixing chambers are arranged horizontally and together form a cylinder, the axis of which is horizontal.

The internal diameter of the individual chambers is -3 110 mm and the internal volume of each chamber is 2.5.10 10 m3. The internal diameter of the pipe for the water supply of the connecting hoses between the entrainment chamber and the mixing chamber and between the mixing chambers and the pipe for the removal of diluted product are the same; The connecting hoses between the chambers and their nozzles have an internal diameter of - 15-15 mm. The length of the hoses is always 40 cm.

In the entraining chamber of the mixer, a polymer spray nozzle with a 2 mm diameter orifice, 10 1 / hour preparation according to example I (polymer emulsion) is pulsed at a frequency of 20 50 sec and through a water nozzle with a 15 mm opening, provided with a check valve diameter 2000 1 / hour water pumped. The speed of the water at the nozzle opening is 3.2 m / sec (* Re 47000) and it rinses the entire polymer nozzle.

The dilute product 25 coming from the mixer is a ready-to-use aqueous solution of the polymer and is suitable for papermaking.

Dilution example II

The procedure is as described in Example 1, 30, but a mixer according to Figure 2 (and 2a) is used, in which the polymer nozzle has 6 openings of 1 mm diameter each, and 5 µl / hour polymer emulsion according to Example 1 is pumped into the mixer.

The dilute product from the mixer is a ready-to-use aqueous solution of the polymer and is suitable for papermaking.

8300326 «4 46

Application example A.

- A 2% aqueous paper slurry of the following composition, expressed as a solid, is used: 100 parts of bleached sulphite pulp 5 20 parts of kaolin 3 parts of resin glue 2 parts of aluminum sulphate For the formation of leaves on the Rapid-Köthen sheet former, 250 ml of test substance with 5, 10, 10, 15 and 20 ml of a 0.0125% aqueous dilution of the product according to Example 1 and mixed with 750 ml of dilution water, respectively. After stirring for 5 seconds at 250 rpm, the dust / water mixture is introduced into the filling chamber of the leaf former (Rapid-Köthen system), whereby 3 liters of water are first introduced into the filling chamber 15. After a residence time of 20 seconds, the blade is formed by operating the suction valve. These are ashed after drying and conditioning of the test sheets. The ash content is related to the filler used and expressed in% retention. The result is summarized in the following Table 20. The given values for% as and% retention are each mean values of two determinations.

Added how- Concentration flake% ash% retention quantity in ml agent * in% (amount 25 0.0125% solution pulled on dry paper dust) _ 5 0.0125 13.31 79.9 10 0.025 14.34 86 .0 15 0.03.75 14.66 88.0 30 20 0.05 14.73 88.4 zero value _-_ 8.51_51.1 * (polymer emulsion)

Application example B

200 parts of dirt sludge suspension with 5% dry 8300326 * 4 47 dust content are first mixed with w parts of a 0.23% aqueous dilution of the preparation prepared according to example I and then for ten seconds with a "Triton". stirrer at a speed of 1000 rpm. The sludge slurry is then filtered directly on a dust filter and the mean value of the volume of the filtrate is determined after 30, 60, 90, 120 and 180 seconds.

W_Average value of volume 10 0 1.5 volume parts 13 15.3 15 40.4 „17 49.1 19_81.9 __ 15

Analogously, as described in Application Examples A and B, the products of Examples II-XXII can be used. 1 8300326

Claims (14)

Water-thinnable, polymerisate and surfactant-containing compositions, characterized in that they: a) contain a hydrophilic cationic polymerisate and 5 M an anionic surfactant, the molar content of anionic surfactant b) not exceeding the molar proportion of cationic monomer units of polymerisate a) and wherein the cation of the polymerisate and the anion of the anionic surfactant can be combined with each other under salt formation. 2. Preparations according to claim 1, characterized in that as further essential components c) an oil immiscible with water, in which the polymerisate is not soluble, but finely divided therein and optionally d) a hypophilic or oil-soluble, non-ionic surfactant and / or e) water 20 and optionally f) an oil-miscible, water-insoluble and not self-dispersible polar solvent, which in itself does not exhibit emulsifying properties, but lowers the water / oil interface tension. Preparations according to claims 1-2, characterized in that at c) is a mixture of oils c ^} and selected so that the Ο / ΐΓ-EHLB value of Cj) is greater than the O / W -EHLB value of the mixture Cj) + c ^). Preparations according to claims 1 to 3 8300326 - 49 - characterized in that they have at least 0.01% wt. %, advantageously * contain at least 0.1 wt% and preferably at least 10 wt% component a). 5. Vinyl-like monomer salts, characterized in that Bet cation is that of a vinyl-like cationic monomer and the anion is that of an anionic surfactant. W / O Emulsions, characterized in that they contain the monomer salts according to claim 5, optionally in addition to emulsifier 10 d), the oil being an oil c) and c) and d) as defined in claim 2. 7. Hydrophilic cationic polymerisates, characterized in that part of the cationic groups is present in a salt form, in which the anion is that of an anionic surfactant. 8. Process for preparing preparations according to claim 1, characterized in that the anionic surfactant b) is combined with the polymerisate a) before, during and / or after the polymerization a) or with the corresponding monomers. 9. Process according to claim 8 for the preparation of preparations according to claims 1-4, characterized in that one of) is a dispersion in oil, which contains a hydrophilic, cationic polymerisate (a), water (e) and a lipophilic or oil-soluble nonionic surfactant (d) contains, with a lipophilic or oil-soluble, substantially insoluble, anionic surfactant (bj), wherein (b}) is a sulfonated hydrocarbon, optionally in salt form, and the oil of the dispersion in oil is an oil (c ^), i.e. a water-immiscible hydrocarbon oil, in which the polymerisate (a) is not soluble, but is finely divided therein with the water and optionally component f] together with b ^) and / or b ^) or add oil solution c ^), 8300326 - 50 - - - * or * β) for the preparation of preparations containing as a), aj) cationic polymerisates of vinyl-like monomers, the to form the cationic po lymerisates a ^) 5 required monomers in the presence of anionic surfactants in W / O emulsion polymerize and optionally distill water and / or oil and optionally further additives a), h), c), d), e) and / or f), or proceeds according to variant), wherein at least a part of the cationic monomers is present as monomer salts according to claim 5 or)) for the preparation of preparations comprising as a), 55 aj,) copolymers of cationic and nonionic vinyl-like monomers contain the nonionic monomers, or part thereof, by the reverse emulsion polymerization process in the presence of c), d) and e) prepolymerize, and after addition of the cationic monomers and Optionally polymerizing the remainder of the nonionic monomers in the presence of b) to the end, wherein b) before, after or together with the cationic monomers and / or in the form of monomer salts, in which the surfactant anion is the counterion of the monomer cation is added. Use of the compositions according to claims 1-4 as a flocculant. Use according to claim 10 for the manufacture of paper and / or for wastewater treatment. Paper obtained according to claim 11. 13. Method for continuously mixing water with a preparation according to claims 1-4, which is pumped hair, characterized in that the preparation is led through at least one sprayer 1 into a water flow in such a way that the water flow circulates sprayer 1, where the volume is 8300326 - 51 -. The flow of water is greater than the volume flow of the preparation * and the velocity of the water is so much higher than the velocity of the preparation that the preparation is dragged along by the water flow such that the adhesion and / or or cohesive forces in the preparation are at least partially overcome, but in principle no shear forces are generated in the flow in such a way that the polymer molecules in the preparation are thereby reduced, the product-water mixture is then accelerated through a narrowed pipe and then in a dilated mixing zone again decelerates with acceleration and deceleration being carried out so many times until the desired distribution of the composition in the water is achieved and after the composition and dilution water come into contact, the process is carried out without using filters or sieves. Device for carrying out the method according to claim 13, characterized by a tube 2 provided with a sprayer 1 for supplying the pumpable preparation, a tube 3 for supplying the water, a conduit 4 for diluting the mixture, a delay zone 5 and a pipe 20 6 for the extraction of the product diluted with water, in particular according to figure 1. 1 8300326