CH660015A5 - PREPARATIONS CONTAINING POLYMER AND SURFACTANTS, THEIR PRODUCTION AND USE. - Google Patents

Description

The invention relates to such preparations, their preparation, their dilution with water and their use, 20 as well as the products obtained by using the preparations and the new monomer and polymer salts.

A first subject of the invention is therefore water-dilutable, polymer- and surfactant-containing preparations, which are characterized in that they contain 25 a) a hydrophilic cationic polymer and b) an anionic surfactant, which is a sulfonated hydrocarbon, the molar proportion of anionic surfactant b) is not greater than the molar proportion of cationic monomer units of polymer a) and 30, whereby the cation of the polymer and the anion of the anionic surfactant can be combined to form salt.

The hydrophilic polymers a) are cationic, i.e. they are free from anionic monomer components, or they can be obtained by polymerizing exclusively cationic and possibly non-ionic monomers.

Any cationic, addition and condensation polymers are suitable as hydrophilic, cationic polymers a), e.g. the polyamidamine, polyethyleneimine-40 and / or polyetheramine series, e.g. in U.S. Patents 3,210,308, 3,275,588, 3,329,657, 3,753,931 and 4,056,510 and French Patent 1,583,363 and / or preferably homo- and copolymers of vinyl-like cationic and optionally non-ionic monomers. 45 ren. As cationic polymers or as cationic monomers here are generally meant both those which already contain cations and those in which the cation is formed only in the presence of water and / or acid but is free from anionic monomers.

so The polymers a) occurring in the preparations according to the invention are preferably at least partially. aj) cationic homo- and / or copolymers of vinyl-like cationic and optionally non-ionic monomers, the polymers a) advantageously consisting mainly of a]); the proportion a ^ in a) is preferably at least 70% by weight, in particular at least 90% by weight; a) particularly preferably consists exclusively of a,).

Preferred monomers for the preparation of aj) are vi-60 nyl-like, water-soluble monomers, primarily those of the acrylic and methacrylic acid ester series, the acrylic and methacrylic acid amide series, the vinylpyridine series, the di-allylamine series, the N-vinylpyrrolidone series and those of the vinyl ether series.

65 Preferred representatives of the above-mentioned classes of monomers are among the cationic types “dialkylaminoalkyl acrylates, trialkylammonium alkyl acrylates, dialkylaminoalkyl methacrylates, methacrylates,

3rd

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retrialkylammonium alkyl esters, acrylic acid dialkylamino hydroalkyl esters, acrylic acid trialkylammonium hydroxyal alkyl esters, methacrylic acid dialkylaminohydroxy alkyl esters, methacrylic acid trialkylammonium hydroxyalkyl esters, 2- and 4-vinylpyridine and the corresponding N-alkylpyridinium derivatives nylammonyl derivative nylammonylamides, nylamylkidylammonium derivatives, nylamylkidylammonium derivatives, nylamylkidylammonium derivatives, nylamylkidylammonium derivatives, nylamylkidylammonium derivatives, nylamylkidylammonium derivatives, nylamylkidylammonium derivatives; -alkylamides, acrylic acid trialkylammoniumalkylamides, methacrylic acid dialkylaminoalkylamides, methacrylic acid trialkylammoniumalkylamides, acrylic acid dialkylsulfoniumalkyl esters and methacrylic acid dialkylsulfonium alkyl esters. The alkylene bridge members (namely between N and O, between O and S and between N and N) advantageously contain 2 to 4, preferably 2 to 3, carbon atoms; the terminal alkyl groups (specifically the substituents on the basic nitrogen or sulfur) advantageously contain 1 to 4, preferably 1 to 2, carbon atoms and can optionally be substituted by phenyl; if they are substituted by phenyl, benzyl is particularly suitable; however, the alkyl radicals are preferably unsubstituted.

Among the cationic monomers mentioned, those of the following formulas are particularly preferred:

CH,

✓R2

= c-co-o-ch2-ch2-nc I Nt3

Ri ch2 = c-co-o-ch2-ch, -n © -r3

I '^ r4

R.

ae

(I),

(II),

wherein

Ri is hydrogen or methyl,

R2 methyl or ethyl,

R3 is methyl or ethyl,

5 R4 hydrogen, methyl or ethyl,

Ae is a counter ion to the ammonium group and n is 2 or 3.

The symbol Ae generally stands for any anion, as is customary for ammonium compounds, partly for a halide ion (in particular chloride, bromide or iodide) or for an R4S04e anion. The symbols R2 and R3 preferably each represent methyl; the symbol R4 also preferably represents methyl. In a particular embodiment of the invention, Ae also stands for i5 (A]) e, i.e. for the anion of an anionic, advantageously lipophilic, preferably oil-soluble surfactant as defined below.

Among the cationic monomer units, the acrylic and methacrylic acid derivatives are generally preferred, especially the optionally quaternized acrylic or methacrylic acid dialkylaminoalkyl esters and dialkylaminoalkylamides; or among the listed monomer compounds, those of the formulas (I) to (VI), in particular those of the formulas (I), (II), (V) and (VI) 25, are preferred. Particularly preferred cationic monomers are those of the formulas (I) and (II).

Preferred representatives of the classes of nonionic monomers mentioned are those of the following formulas

30th

ch2 = c-conh2

I.

r,

ch, = c-co-o-ch2-choh-ch2-n ^

f R

Ri r?

(III), 35

■ 3

CH = CH-2

/ R2

ch, = c-c0-0-chn-ch0h-ch2-n® ~ R3 Ae k

A

ch2 = c-co-nh- (ch2) n-i <

I \ 3

R>

R2

ch2 = c-co-nh- (ch2) n-n® ~ r3 a ©

ch2 = ch-o-r5 (ÏV), 40 and ch2 = c-co-nh-c (ch3) 2-ch2-co-ch3

(XIII),

(XIV),

(XV)

(XVI),

(V), 45

r,

I.

R.

ch2 = ch ~ ch2 \

ch2 = ch-ch ^

X

R4

NO,

(vi), 50

(VII), 55

ch2 = ch-ch2 r,,

\ N® A © ch2 = ch-ch2 xr4

(VIII),

60

ch2-ch ch2 = CH

ch2-CH

and

(ix),

(x),

(XII)

wherein

R5 means methyl or ethyl and

R, which has the meaning given above.

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

Preferred polymers a 0 are copolymers of cationic monomers of the formula (I) and / or (II) and nonionic monomers of the formula (XIII).

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

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4th

Monomer units is advantageously 5 to 20 mol%; Suitable stronger cationic polymers are those whose proportion of cationic monomer units is advantageously 20 to 80 mol%, preferably 30 to 60 mol%.

The average molecular weight (weight average) of the polymers can be as high as desired, e.g. up to 20,000,000; they advantageously have an average molecular weight of 2: 100,000, preferably ^ 500,000, particularly preferably 2: 1,000,000.

Any conventional hydrocarbon components which contain at least one lipophilic hydrocarbon radical, such as those e.g. in “Surfactant Science Sériés” (M. Dekker Inc., New York and Basel), vol. 7: "Anionic Surfactants" (edited by Warner M. Linfield, 1976) - parts 1 and 2 - are described; the lipophilic radical is preferably araliphatic or aliphatic and advantageously contains at least 9 carbon atoms, preferably 12-36 carbon atoms.

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

The anionic surfactants are advantageously at least partially in the form of salt, any conventional cations being suitable for salt formation, e.g. Alkali metal cations (lithium, sodium, potassium), ammonium cations [both unsubstituted ammonium and substituted ammonium, e.g. Mono-, di- and tri- (C] _8-alkyl) -ammonium and mono-, di- and tri- (C2 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 other polyvalent cations, in particular Zn2 +, Al3 + and Zr4 +. The anionic surfactants are preferably in the form of the corresponding salts of polyvalent inorganic cations, of which calcium is particularly preferred.

The anionic surfactants can have a more or less pronounced water solubility or dispersibility or can be practically insoluble in water (ie they do not give any real solution in water at the concentrations used, but can still be dispersible in water and / or preferably in oil be dispersible or soluble), which essentially depends on the choice of the lipophilic residue and on the choice of the cation. Preferred anionic surfactants are the lipophilic, preferably those which are oil-soluble in the form of the Na salt, in particular those which are in the form of salts of such cations (preferably polyvalent inorganic cations) that they do not give any real solutions in water and with water and with give W / O emulsions to the corresponding oils, in particular as defined below under c), ie they have W / O emulsifier character or are W / O emulsifiers.

The above-mentioned anionic surfactants are generally known or can be prepared in a manner known per se. The amine salts and the salts of polyvalent inorganic cations of the anionic surfactants are e.g. advantageously produced in situ by advantageously reacting the alkali metal salts of these surfactants with water-soluble salts of the corresponding amines or the polyvalent inorganic cations. Suitable water-soluble salts are essentially salts of strong inorganic acids (depending on the cation, advantageously sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid) and simple organic carboxylic acids (Ci 4-carboxylic acids, primarily formic acid and acetic acid), the sulfates, chlorides and Acetates are preferred and the formates and especially the chlorides are preferred among the salts of the polyvalent inorganic cations. Calcium chloride is particularly preferably used.

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

In general, the polymers in the preparations according to the invention contain cationic monomer units io and, if appropriate, nonionic monomer units, part of the cationic monomer units containing the anion of the anionic surfactant as counterion to the cation. The polymers can be shown schematically as those which contain the following recurring monomer units:

-Q-

i

(Kat®) (A, e)

20th

25th

30th

-Q-

I.

(Kat®) (A, ©)

and if necessary

-G-

wherein

(a),

(ß)

(y)

(a) and (β) are cationic monomer units, i.e. recurring cationic units derived from cationic monomers

(y) i.e. -G- are non-ionic monomer units, i.e. 35 recurring non-ionic units derived from non-ionic monomers

Q means the part of the monomer unit which is involved in the backbone and Kat® means the cationic part bound to it, and 40 (A) 0) is a surfactant and (A2e) is a non-surfactant anion.

Preferred monomer units (a) and (β) each correspond to the formulas

45

R,

i

-ch2-c-

(<* l)

50

and

55 -CH, -C-

(Kat®) (A, e)

Ri

!

(ß>)

(Kat®) (A2e)

where (ai) and (ß,) or (Kat®) are preferably those radicals 60 such as those derived from the formulas of the formulas (II), (IV), (VI), (Vili), (XI) and (XII) correspond. A] 9 is preferably the anion of one of the surfactants mentioned above, advantageously of a lipophilic surfactant (as defined above), in particular of one of the sulfonates mentioned. A2e preferably represents one of the non-surfactant anions mentioned above, as e.g. is formed by quaternization and / or protonation, preferably halide or R40-S03e.

(A) or (a,) is particularly preferably

5

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-CH2-Ç-

© / R2

or for

-CH2-

C0-0-CH2-Ctl2-N-R3

xr "

fl

(Aai0)

(02)

Ì ® / Kz

C0-NH- {CH2>? J-N-R3

NR4

(Aaj6) (a3)

wherein Aaj © is the anion of a petroleum sulfonate, in particular of a lipophilic petroleum sulfonate. 15

Preferred monomer units (ß) or (ßt) correspond to the formulas

Consideration; synthetic oils include both synthetic hydrocarbons and modified paraffins (hydrocarbons) and fatty acid esters (primarily triglycerides and monoesters).

5 Individual, preferred categories of oils are the following:

1. Hydrocarbons 1.1 Hydrocarbons from petroleum processing, mainly

1.1.1 Special gasoline, which is distilled out of the raw gasoline (boiling range 65-140 ° C) (dearomatized and aromatic-containing types)

1.1.2 White spirits, white spirit and mineral spirits (boiling range 100-310 ° C, preferably 140-300 C), in particular:

and

-CH2 — V— R

: O-O-ch2-CH2-N-R3 XR4

(Aa2 <3)

(ß2)

-CH2 — j—

CO-NH- (CH2) n-f (- R3

Xr4

(Aa26)

(ß3),

30th

where Aa2e is chloride or R40-S03e.

Preferred monomer units (y) are those which correspond to the derivatives of the monomers of the above formulas 35 (XIII) to (XVI), preferably those of the formula

R,

I.

-CH2-C-

(Yi)

, 40

co-nh2

especially the formula

-ch2-ch-

I.

co-nh2

• aromatics-free types boiling range 100-270 "C

preferably 140-250 C.

• Fractions with an aroma content between 12 and 19% boiling range 160-210 C.

• Fractions with an aromatic content between 24 and 45% boiling range 140-310 C.

• fractions with an aromatic content of 80-90%

Boiling range 160-260 C.

• purely aromatic white spirits boiling range 160-310 C

1.1.3 Aromatic-free hydrocarbons with an isoparaffinic structure (boiling range 110-260 ° C)

1.1.4 Paraffin oils (= mineral oils) e.g. Diesel oils, spindle oils, machine oils, cylinder oils, lubricating oils and petroleum jelly oils

1.1.5 Petrolatum (Petrolate)

1.2 Synthesis of hydrocarbons, primarily those from Fischer-Tropsch synthesis or high-pressure coal hydrogenation, in particular:

- synthetic gasoline boiling range 65-170 C.

- Kogasin I boiling range 190-230 C.

- Kogasin II boiling range 230-330 C.

- synthetic paraffin oil boiling range 300-450 ° C

1.3 If necessary, alkyl-substituted benzenes, mainly benzene, xylene, toluene, methyl ethyl and trimethyl benzenes, dimethyl ethyl and tetramethyl benzenes, as well as higher alkylbenzenes (Q-C, 2-alkylbenzenes).

(72).

Preferred polymers are those which contain or consist of the units (ai), (Pî) and (yi), in particular those which contain or consist of the units (a2), (β2) and (y2)

The preparations also advantageously contain:

c) a water-immiscible oil in which the polymer is not soluble but is finely divided therein.

In this case in particular, it is advantageous that the anionic surfactant b)

b ') is a lipophilic, preferably oil-soluble, anionic surfactant.

Component c) can be either a uniform oil or a mixture of different oils. In general, any oils, such as are used for the production of water-soluble polymer-containing emulsions and / or dispersions, are suitable, both natural and synthetic oils. Oils from the processing of petroleum as well as vegetable and animal oils (mainly triglycerides) come in as natural oils

2. Natural vegetable or animal triglycerides, in particular olive oil, peanut oil, cotton oil, coconut fat, turnip oil,

45 sunflower oil, corn oil, castor oil and claw oil.

3. Fatty acid monoesters, primarily Ci_4 alkyl esters of Cj2-24-5, preferably C14_24 fatty acids, in particular: methyl, butyl and isopropyl esters of stearic acid, oleic acid, palmitic acid and myristic acid and mixtures thereof.

50 The petrolates are advantageously used in a mixture with oils that are liquid at room temperature (20 ° C).

Among the oils mentioned, the most largely aromatic-free hydrocarbons and the aliphatic fatty acid esters are preferred, in particular the hydrocarbon 55 substances, including those according to sections 1.1.2, 1.1.3 and 1.1.4, and above all aromatic-free and low-aromatic white spirits, isoparaffinic oils (1.1.3) and mineral oils (1.1.4) are preferred.

A special aspect of the invention is that 60 c) is a mixture of at least two oils, in particular a mixture of an oil q) and an oil c2), which are chosen such that the O / W-EHLB value of the oil Cj) is greater than the O / W-EHLB value of the mixture of oils e,) + c2). O / W-EHLB value means the optimal HLB value 65 of a hypothetical surfactant which is required for this oil or oil mixture so that a stable oil-in-water emulsion can form; see e.g. “Cosmetics, Science and Technology”, published by John Wiley and Sons (2nd edition, vol.

660 015

6

3,1974), pages 602-607, or Philipp Shermann “Emulsion Science”, Academic Press, London and New York, 1968, pages 146-147, or Paul Becher “Emulsion, Theory and Practice”, 2nd édition, 1965, American Chemical Society, Monograph Series no. 162.

The O / W-EHLB value of the oil c2) is preferably smaller than that of the oil c ^.

Preferred oils Cj) have an O / W EHLB value in the range from 10 to 15; such oils are among those listed above, especially those mentioned in Sections 1.1.1.1.1.2.1.1.3 and 1.3. Preferred oils c2) have an O / W EHLB value of 7 to 10; such oils are, among those enumerated above, especially those mentioned in Sections 1.1.4.1.1.5, 2 and 3.

In addition to surfactant b), the preparations according to the invention can also contain nonionic surfactants; these are expediently lipophilic.

The preparations according to the invention thus advantageously comprise d) a lipophilic, preferably oil-soluble, nonionic surfactant.

This component d) can be a uniform surfactant or a mixture of lipophilic or oil-soluble, non-ionic surfactants. Component d) is expediently a W / O (water-in-oil) emulsifier, i.e. a surfactant which is capable of producing a W / O emulsion with at least some of the oils c) in the presence of water.

The nonionic surfactants d) are advantageously water-insoluble or only dispersible in water and, as W / O emulsifiers, advantageously have an HBL value ^ 8, preferably between 3 and 8; the HLB value is particularly preferably between 4 and 7.

If d) is a mixture of non-ionogenic lipophilic surfactants, the individual components of this mixture d) can also have different HLB values, but are then used in such relative amounts that the average HLB value of this surfactant mixture is advantageous ^ 8 and is preferably between 3 and 8, in particular between 4 and 7.

As component d), i.e. Suitable lipophilic, preferably oil-soluble, nonionic surfactants are generally conventional compounds, essentially those which contain at least one lipophilic hydrocarbon radical, advantageously with at least 9, preferably 9-24, carbon atoms and at least one nonionic hydrophilic radical, which advantageously is a mono- or polyethylene-glycol residue optionally containing propylene glycol units and / or the residue of a higher polyol (eg glycerol, mannitol or sorbitol); these lipophilic or oil-soluble surfactants can also be referred to as hydrophobic surfactants and among the hydrophobic surfactants also the hydrophobic pluronic types and tetronics can be mentioned, in which the high proportion of polypropylene glycol can be referred to as a lipophilic residue. The following categories of non-ionic surfactants can be mentioned:

Mono- or polyoxyethylation 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; or 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 propyleneoxy units (Pluronic types) and ethylene oxide / propylene oxide addition

Products of ethylenediamine, with a high proportion of propyleneoxy units (Tetronic types), which are considered non-ionic surfactants due to the high proportion of propyleneoxy units.

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

Preferred nonionic surfactants are generally mono- and / or polyoxyethylation products of aliphatic alcohols, of alkylphenols and of aliphatic solid acids, polyol partial esters of aliphatic fatty acids, mono- and / or diethers of mono- and / or polyethylene glycols with aliphatic alcohols and / or alkylpheno-15 oils and mono- and / or diesters of mono- and / or poly-ethylene glycols with aliphatic fatty acids.

The fatty acid residues which occur can generally be acyl residues of conventional alkylcarboxylic acids or alkenylcarboxylic acids, 20 monoethylenically unsaturated acids advantageously being considered as alkenylcarboxylic acids. The alkyl residues as the only lipophilic residues [such as e.g. in formula (XVII) below 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 residues, e.g. in the remainder of formula (a) below, the alkyl radicals advantageously contain 4-12 carbon atoms and can also be linear or branched. If the lipophilic residue is the acyl residue of a carboxylic acid, then it is advantageously the residue of a fatty acid, essentially an alkyl or alkenyl carboxylic acid which advantageously contains 9-24, preferably 12-20, carbon atoms, with lauric acid, myristic acid, Stearic acid and oleic acid are particularly preferred. The polyethylene glycol derivatives, especially 35 of the formulas below, are generally average formulas, i.e. those in which the specified number of ethyleneoxy units is an average number.

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

RHO-CH2-CH2) p-OH and

(R ^ CO) q-X where

(XVII)

(XVIII),

R6 is C9_24-alkyl or alkenyl or a radical of the formula

50

v 8 f

(a),

55

R, -CO-each the acyl radical of an alkyl or alkenyl carboxylic acid with 12-20 carbon atoms,

R-8 C4_i2 alkyl,

X is the q-valent radical of glycerol or sorbitol or egg-60 nes mono- or polyethylene glycol of the formula

H0- (CH2-CH2-0) s-H (XIX),

p 1 to 6,

65 q 1 or 2, or 3 for sorbitol,

r 1 or 2 and s represent 1 to 10, the number and length of the lipophilic radicals and number of -CH2-CH2-0 groups expediently so

7

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can be chosen so that the HLB value of the non-ionic emulsifier or emulsifier mixture is between 3 and 8, preferably between 4 and 7.

Among them, those of the following formulas are preferred

R <J- (0-CH2-CH2) I-0H

(XX),

Holes advantageously contain 5-10 carbon atoms per hydroxy group and the following can be mentioned in particular: methyl isobutyl carbinol, 2-ethylhexanol, isononanol, isodecanol and 2,4,7,9-tetramethyl-5-decyn-5 4.7 -diol. Among the phosphoric acid triesters, tributyl phosphate, triisobutyl phosphate and tri- (butoxyethyl) phosphate can be mentioned in particular. Among the Pluro-nics, the Pluronic L101 can be mentioned in particular.

(0 "CH2-CH2) F0H

R10-CO-Y and r, 0-co-o- (ch2-ch2-o) m-co-r10

(XXI),

(XXII)

10th

(XXIII),

20th

25th

wherein

R9 C9. i8-alkyl or alkenyl,

Rio-CO- the acyl residue of an aliphatic C12_] 8 fatty acid,

Y- the monovalent residue of sorbitol, glycerol or di to tetraethylene glycol,

12 to 3,

k is 3 to 5 and m is 4 to 9.

The HLB value of the non-ionic surfactants can be determined by a simple known formula, with knowledge of the lipophilic residue of the hydrophilic residue and the number of ethyleneoxy or. Propyleneoxy units. If the calculated value for a non-ionic surfactant is 2.5 or less, then it is no longer regarded as a W / O emulsifier.

If c) is a mixture of oils Cj) and c2), then the surfactants d) and the oils are advantageously chosen so that the O / W-EHLB of the mixture q) + c2) is as close as possible to the HLB value of d) but is advantageously not less than this.

The preparations according to the invention advantageously also contain e) water.

The polymers a) or the polymer salts thereof, which contain the anion of the anionic surfactant as counter ion, are hydrophilic, i.e. they can absorb water or form a gel or sol in the presence of water or are at least colloidally soluble in water; the relative amount of water used with the oil (c) and with the emulsifier (d) is generally chosen so that the polymer is finely dispersed in the oil together with the water (whether as a suspension of the polymer with) water taken up or the water-swollen polymer or the aqueous polymer gel in the oil, be it as an emulsion of the aqueous polymer sol or the aqueous polymer solution in the oil).

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

These solvents are generally polar compounds which have an extremely low HLB value but are still sufficiently polar to attach to the oil / water interface; these are advantageously water-insoluble, aliphatic alcohols or phosphoric acid triesters or Pluronics. The Alko

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

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

A particular subject of the invention is the process for the preparation of preparations according to the invention which contain polymers aO, which is characterized in that the monomers required for the formation of the polymers a]) are polymerized in the presence of anionic surfactants in a W / O emulsion and, if desired Water and / or oil are distilled off and, if appropriate, further additives a), b), c), d), e) and / or 0 are added.

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

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Ri

I.

CH2-C- (Kat®) (A, e) (XXIV)

Preferred salts according to the invention are those in which the cation is such as in the formulas (II), (IV), (VI), (VIII), (XI) and (XII); Particularly preferred salts according to the invention are those of the formulas (II), (IV) and (VI), in which the counterions are those of the above-mentioned anionic surfactants A, 0, in particular hydrocarbon sulfonates, in particular petroleum sulfonates.

Preferred monomer salts according to the invention correspond to the formulas

CH2 = C-CO-NH- (CH2) n-N © ^ 3 (Aa,) e (XXV)

I.

and particularly

CH2 = C-C0-0-CH2-CH2-N®-R3 (Aa,) e (XXVI) I \ r.

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

A particular embodiment of the production process for the polymer-containing preparations according to the invention consists in that an oily dispersion which comprises a hydrophilic, cationic polymer (a), water (e) and a lipophilic or oil-soluble, nonionic surfactant (d) but not an anionic Surfactant contains a lipophilic, preferably oil-soluble, practically water-insoluble, anionic surfactant (b)), where (b [) is a sulfonated hydrocarbon, optionally in salt form, and the oil of the oily dispersion is an oil (c3), ie a water-immiscible hydrocarbon oil in which the polymer (a) is not soluble, but is finely divided therein with the water. The polymers (a) here are preferably vinyl-like polymers (a]) as described above. Suitable hydrocarbon oils (c3) are generally those as described in subsection 1.1, of which those according to corresponding subsections 1.1.1 to 1.1.4, in particular 1.1.3, 1.1.4 and above all white spirits are preferred.

The oily dispersions which contain (a ^ in addition to (e), (c3) and (d) but no (b)) are advantageously prepared by emulsion polymerizing corresponding aqueous monomer solutions in the oil and in the presence of the emulsifier (d) and, if appropriate, partially distilling off water .

The polymerization can be carried out in a manner known per se (see, for example, “High Polymers”, vol. 9, 1955 “Emulsion Polymerization”, publisher: Interscience Publisher Inc., New York) and the aqueous system can, in addition to the particular constituents required according to the invention, Contain usual additives, such as Polymerization initiators (preferably compounds which form free radicals with thermal addition or a redox system), complexing agents (e.g. Na-EDTA), acids and / or bases for pH adjustment and / or metal salts, e.g. Na + and / or Ca2 + salts. After inerting (i.e. after displacing the oxygen with an inert gas) and after adding suitable polymerization initiators, the polymerization takes place. After emulsion polymerization has taken place, or after anionic surfactants and cationic polymers have been brought together, in particular after dilution with water, cationic groups in the corresponding salt form can also be present in the polymer. The polymerization is normally exothermic and takes place e.g. 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 wt .-% (based on the total emulsion). The polymerization can be carried out adiabatically or isothermally, but it is preferably carried out partially adiabatically, i.e. the temperature is allowed to rise to a limited extent by metered addition of the initiator and / or by cooling the reaction mixture, advantageously up to 120 ° C., if appropriate under pressure; the procedure is preferably between 30 and 110 ° C. If the mixture to be polymerized contains hydrolyzable monomers (in particular esters or primary amides), then such reaction conditions are expediently chosen that hydrolysis to the undesired acids is avoided as far as possible.

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

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

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

Should the preparation contain a mixture of oils q) and c2)?

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hold, then the emulsion polymerization is advantageously carried out in oil C]), which optionally contains c2); The oil c2) or the possibly remaining part of the oil c2) can, if necessary, be added after the emulsion polymerization has taken place, if appropriate after the water has been distilled off, or most of the water.

The quantitative composition of the preferred preparations according to the invention and obtainable as described above can advantageously be schematized as follows: the preparation contains per 100 parts by weight of component a)

x parts by weight of component b)

y parts by weight of component c)

z parts by weight of component d)

u parts by weight of component e) and v parts by weight of component f).

The concentration x and z preferably correspond at least to those required so that the aqueous monomer-containing dispersion remains sufficiently stable during the polymerization; x is advantageously at least 0.5, primarily 1-30, preferably 1.0-15, in particular 1.5-10. The quantitative ratios of a) and b) given above refer to the respective components without taking into account a corresponding salt formation in the numbers 100 for a) and x for b), but should include the possible salt formation of a) + b); z is advantageously 0-80, preferably 1-80, particularly preferably 2-30. The preparations according to the invention are advantageously oil-containing and y is preferably 30-400, particularly preferably 40-200. The water content can fluctuate greatly and is partly also on the oil content, i.e. depends on y, to the extent that the preparations according to the invention in the oil-containing form which have not yet been diluted with water, if they contain water, contain this predominantly in the discontinuous phase, i.e. Oil is the continuous phase and the water-containing phase is dispersed or emulsified in it. After the (inverse) emulsion polymerization, the water can be distilled off, advantageously azeotropically, in theory all the water can be distilled off, i.e. up to u = 0, but this is practically not preferred since it is difficult to completely distill off the residual water swelling the polymer; on the other hand, the polymer-containing W / O emulsion may also contain water, e.g. also in the form of a further W / O emulsion or an aqueous solution of a polymer a), are added, so that the water content of the preparation can also be relatively high; u is advantageously 0 ^ 300, preferably 1-300, particularly preferably 2-200. From an economic point of view, it is preferable not to distill off all the water and the water content u is advantageously 5 to 300, preferably 10 to 200.

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

The preparations according to the invention advantageously have the following composition: per 100 parts a)

x = 1-30 y = 30-400 z = 1-80 u = 0-300

v = 0-30, (where v <y)

A particularly preferred composition of the preparations according to the invention is as follows: per 100 parts a)

x = x '= 1.5-10 y = y' = 40-200 z = z '= 2-30 u = u' = 2-200 5 v = v '= 0-15, and v' <

The oil-containing preparations according to the invention are dispersions which can have very different viscosities and it is also possible to produce very low-viscosity preparations; the viscosity (Brookfield rotational viscosity, measured in an LV viscometer) of the dispersions e.g. vary between 5 cp (spindle no. 2) and 10,000 cp (spindle no. 4), preferably between 50 cp (spindle no. 2) and 5000 cp (spindle no. 4); the dispersions according to the invention are also stable, i.e. they can be stored for a long time without change, or, if the dispersions separate into layers, they can be brought into the original, regularly dispersed form by simple stirring. Particularly noteworthy is the very good dispersibility in water or dilutability with water of the preparations according to the invention, in particular the preparations containing c), and indeed they can be diluted very quickly by simply adding the preparations to water or from water to the preparations with stirring turn 25 or the usual dilution devices, as are common in the art and are also widely described in the literature, can be used for a pre-dilution with water. Diluents working with water jet pumps are particularly suitable, i.e. the polymer dispersion is pumped through a nozzle and the water through another nozzle into a «chamber» in such a way that the water entrains the dispersion at high speed, after which the mixture in various ways, e.g.

is distributed in the water via baffle plates or walls or by using high shear forces or by pumping in and out in «rest tanks». A particularly valuable method for diluting the dispersions according to the invention with water is characterized in that the dispersion is introduced into a water flow through at least one nozzle © in such a way that the water flow flows around the nozzle ©, the volume flow of the water being higher than the volume flow of the Dispersion and the speed of the water is so much higher than the speed of the dispersion that the dispersion is pulled along by the water flow in such a way that the adhesion and / or cohesive forces in the dispersion are at least partially overcome, but in the flow in the Essentially no such high shear forces occur that the molecules in the dispersion are crushed, the product-50 water mixture is then accelerated through a narrow pipe and then slowed down again in an expanded mixing zone, with acceleration and deceleration being carried out until the desired distribution of the Pr product is reached in the water and, after the dispersion and the water come into contact with one another, the process is carried out without the use of filters or sieves.

Particularly noteworthy is the apparatus (mixer) for 60 carrying out these dilution processes, which through a line © provided with a nozzle © for feeding the viscous product, a line ® for feeding the water, a line © for the Acceleration of the mixture, a slowdown zone © and a line 65 © for the removal of the product diluted with water is marked.

If an addition in an aqueous medium is required for dilution with water, e.g. a surfactant (especially a

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O / W emulsifier), then this can conveniently e.g. be metered into the line ®.

The entire apparatus is preferably tubular and divided into chambers; the line ® for feeding the water is expediently attached to one end of the apparatus coaxially therewith and the line © for feeding the dispersion is preferably attached to the apparatus at a right angle to the line ®, preferably in such a way that the nozzle © is as close as possible to the mouth of the line ® and is advantageous

that the nozzle surface is between the boundary and the axis of the direct water jet. The first part of the apparatus, i.e. the chamber to which the lines © and ® are attached can also be referred to as a "tear chamber", since there the viscous product that emerges from the nozzle © is drawn in by the water jet ® or is rather carried away. The nozzle © can consist of a single opening, e.g. a round opening or a slot, or can also be a plate with several holes (advantageously 1 to 20 openings with a diameter of 0.2 to 5 mm each), which is particularly preferred in the case of more viscous products, so that through the nozzle already a first distribution of the product takes place. The water flow at the outlet of the line ® 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, in general the highest possible turbulence and speed of the water are preferred; the Reynolds number at the outlet of the tube ® is advantageously between 10,000 and 100,000, preferably between 25,000 and 75,000.

In the second half of the rice chamber, near the end wall, there is a line ©, which can be a pipe or a hose (most simply a hose), the inner cross-section of which is smaller than the inner cross-section of the rice chamber, so that the mixture is accelerated by water and product therein; the inner diameter of the line © is advantageously not less than half the inner diameter of the line ® and not greater than half the inner diameter of the drawing chamber or the mixing chamber; preferably the inner diameter of the line © is equal to that of the line ® ± 50%; the lines ® and © particularly preferably have the same inner diameter. The internal volume of the connecting lines © is advantageously not greater than the internal volume of the tear chamber (R); the connecting lines © are preferably as short as possible (internal volume

R R

<- preferably <-). More than one nozzle for pumping the viscous product can also be installed in the tear chamber; e.g. if the mixer is arranged vertically (i.e. if the dilution water is pumped through the pipe ® vertically from top to bottom or from bottom to top into the mixer), several nozzles may be fitted radially around the axis near the mouth of the line ®, or e.g. If the mixer is arranged horizontally, several nozzles can also be installed one behind the other. The horizontal arrangement of the mixer (see figure) is preferred and pumping the dispersion through a single pipe © is the simplest and preferred. After the diluted mixture has been accelerated through the line ©, it flows into the deceleration zone © or into the mixing chamber (M), where the mixture is preferably slowed down again with the formation of vortices; the mixture emerges from the mixing chamber (M) after further acceleration through a line © or through a further line © (with repeated acceleration). The ratio of the inner diameter of the tube ®, the line © or the line © or © to the inner diameter of the (cylindrical) chamber (R) or (M) is preferably 1: 3 to 51:20.

A schematic representation of such a mixer with a horizontal arrangement of the chambers is shown in Fig. 1. In Fig. 1.1 and 1.2 the essential components are shown as ideal fragments, and indeed in Fig. 1.1 the water is pumped in at the end (A) of the mixer through the pipe ® and in the subsequent part (B) through the pipe © and the nozzle © the viscous product is pumped in: part (B) can be recurring, but preferably (B) is a single part; in part (C) the line 15 is attached and part © of the drawing represents the slowdown zone; the essential part (C) can be recurring; part (C) advantageously occurs 1-10 times, preferably 2-6 times; the lines © occurring several times can have the same diameter or the diameter can also vary, e.g. increase regularly if e.g. the viscosity of the diluted product increases sharply with finer distribution; It is easiest if all of the lines © occurring are identical to one another. Fig. 1.2 shows the same apparatus as in Fig. 1.1, only the division into chambers instead of acceleration and deceleration zones is shown there, i.e. (R) represents the rice chamber consisting of parts (A), (B) and (CO) and (M) represents a mixing chamber that can be recurrent [like part (C) of Fig. 1.1] , Through the line © (or through the line © of the last chamber)

the diluted product is removed; the line © (or the line © of the last chamber) can have the same diameter as the lines © (or like the last 35 of the lines © or a different diameter, for example a somewhat larger diameter (for example up to 50% larger ), while the diluted product is still accelerating in this line A further preferred arrangement of the chambers is shown in Fig. 40 2.

The device can be built in various sizes, e.g. the internal volume of each individual chamber can vary from a few cm3 to about m3, with the corresponding pipes, nozzles and connecting lines being built proportionately; the inner volume of the chambers (R) and (M) can vary up to ± 50% if desired, but the respective chambers are preferably identical to one another in their inner volume. The mixing chambers are advantageously constructed in such a way that they can be attached or detached as individual elements and connected by hoses ©, so that the number of mixing chambers can be varied as required in the same apparatus; it is also expedient if the individual lines ©, ®, © and © or ©, e.g. by nozzles, are attached so that they can be removed as required or exchanged for others with different diameters; the nozzle © is also advantageously attached to the respective pipe © in such a way that it can be replaced as required, in particular depending on the viscosity of the polymer dispersion.

The mixer according to the invention is expediently operated in such a way that it is practically completely filled with liquid and consequently the various liquid flows do not impinge on parts or walls of the mixer, but rather in such a way that vortices form in the liquid. Depending on the solubility or dispersibility of the product and, if appropriate, swelling effect in water (or increase in viscosity), the number of mixing chambers and the diameter of the

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different lines or pipes, as well as the initial speed of the water can be selected and optimized accordingly. A measure of the acceleration and deceleration effect for a given Reynolds number of the inflowing water and for a given apparatus is the pressure drop between the inflowing water and the outflowing diluted product; the minimum necessary pressure drop in order to achieve a good distribution or dilution,

can also vary depending on the product used and is advantageously values ^ 0.2 bar; in the case of a mixer of medium size (internal volume of the mixer of the order of magnitude of 10 ~ 3 to 10_ 1 m3), the procedure is preferably such that the pressure drop 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 with a pressure drop ^ 5 bar or ig 2.5 bar and, with well dilutable products, even with a pressure drop ^ 1.5 bar. Although better dilution effects are achieved with a pressure drop that is as high as possible (i.e. a quicker small distribution), it is preferred for apparatus 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 mixer of medium size in the range of 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 preparations can also be obtained in a few seconds.

30th

Due to the very rapid dilutability with water of the preparations according to the invention, many large-scale, continuously carried out processes in which cationic polymers are used can be carried out very efficiently and with an optimal metering rate. It is also particularly worth mentioning that the preparations according to the invention can have a very high concentration of cationic polymers; the biological eliminability of the preparations can also be mentioned. The preparations according to the invention are distinguished by their dilutability with water and their distributability in water, and the invention comprises such preparations in any concentration, provided that they can still be diluted with water or the polymers are soluble or dispersible or dissolved or dispersed in water; 45 in particular means both more concentrated preparations, especially those which contain at least 10% by weight of cationic polymer, and prediluted preparations, especially those which contain at least 0.001% by weight, preferably at least 0.1% by weight, of cationic polymer contain. 50

. The preparations according to the invention can be used in all fields of technology in which cationic water-soluble polymers are used, in particular they can be used as flocculants and the invention further relates to the use of the 55 preparations according to the invention as flocculants, preferably as retention and drainage agents for paper and as Flocculant for aqueous sludge, especially digested sludge and fresh sludge from municipal sewage treatment plants. The invention also relates to the process for the production of paper, which is characterized in that a preparation according to the invention is used as the retention and / or drainage agent.

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

The required concentration of the preparation for the respective application depends, of course, on the

65

Concentration of active substance (polymer) for the respective flocculation.

The mixer described above can be switched on to any system in which corresponding products diluted with water have to be metered in continuously, in particular systems in which the diluted water-soluble or at least water-dispersible high polymers have to be metered in, such as e.g. Flocculants in wastewater treatment or wastewater treatment, in paper production (especially as retention and / or drainage agents), in the slurrying of drilling sand and / or other minerals in sand or colloidal form or in the recovery of residual oil in the petroleum industry. As a result of the rapid fine distribution of the polymers by this dilution process and with this apparatus, corresponding dilute solutions or dispersions can be obtained even without having to switch on a dwell time or dwell vessels; the corresponding mixer according to the invention can be connected directly to the system.

Another object of the invention is the use of the mixer according to the invention as a dilution station for the polymer dispersions according to the invention in plants in which the corresponding products have to be used as flocculants in diluted form, in particular in papermaking and sewage treatment plants.

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

example 1

43.5 parts of emulsifier (Bi) are mixed with 800.0 parts of water, producing a very fine, opalescent emulsion. Now 8.2 parts of calcium chloride are added to form the calcium salt of (B,). A strong precipitation is immediately observed, which corresponds to the formation of the water-insoluble (oil-soluble) calcium sulfonate. Then 440.0 parts of White Spirit (Q) are added with stirring. A water-in-oil emulsion is formed, which is stabilized by adding 99.5 parts of emulsifier (D,). This water-in-oil emulsion is then in the order given 353.0 parts of a 75% aqueous methacryloyloxyethyltrimethylammonium chloride solution, 454.0 parts of acrylamide, 1.4 parts of ethylenediamine-tetra-acetic acid di-sodium salt, 0.7 Parts of iron (III) sulfate and 0.7 part of tert-butyl hydroperoxide were added. The pH of the aqueous phase is approximately 3.0. The dispersion obtained is then rendered inert with nitrogen and heated to 35.degree. As soon as this temperature is reached, an air-free solution of 2.7 parts of sodium thiosulfate in 50.0 parts of water is started to be added dropwise. The addition takes place 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 has ended. A stable, fine, low-viscosity polymer-containing dispersion is obtained which has a viscosity of 1000 cp (Brookfield, spindle 3, 60 rpm). The product can be diluted very well with water: approx. 30-40 seconds after the addition to cold water, the maximum viscosity is already reached with a 1: 200 (= 0.5%) aqueous dilution. The viscosity of a freshly prepared 1: 100 diluted (= 1%) aqueous preparation is approx. 500 cp (Brookfield, spindle 3, 60 rpm).

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Example 2

454.0 parts of acrylamide, 353.0 parts of a 75% aqueous methacryloyloxyethyltrimethylammonium chloride solution, 1.4 parts of ethylenediaminetetraacetic acid di-sodium salt, 0.7 part of iron (III) sulfate, and 9.8 parts of calcium chloride rid are added in the order given, with stirring, to 600.0 parts of water. The solution obtained is then mixed with a solution of 52.0 parts of emulsifier (Bi) and 80.0 parts of emulsifier (DO in 600.0 parts of White Spirit (CO. A water-in-oil emulsion with a pH builds up -Value (aqueous phase) of 3.0, which is subsequently rendered inert with nitrogen, then 0.7 part of tert-butyl hydroperoxide and then an air-free solution of 1.1 parts of sodium thiosulfate in 12 parts of water are used to initiate the polymerization reaction A strongly exothermic reaction occurs immediately, the temperature rising despite roomy cooling from room temperature to 90 ° C. A thin, polymeric dispersion which is easily dilutable with water is obtained.

Example 3

24 parts of emulsifier (B0 are mixed with 480 parts of water to form a very fine, opalescent emulsion. Now, 564 parts of a 75% strength aqueous methacryloyloxyethyltrimethylammonium chloride solution are added to form the corresponding methacryloyloxyethyltrimethylammonium petroleumsulphonate. Then, in the order given, are added Stir, another 408.30 parts of acrylamide

1.43 parts of ethylenediamine-tetraacetic acid di-sodium salt

0.77 parts iron (III) sulfate 480.0 parts White Spirit (CO 30.0 parts emulsifier (DO 30.0 parts emulsifier (D2)

4.8 parts of calcium chloride, 0.6 parts of tert-butyl hydroperoxide were added. The dispersion obtained is then rendered inert with nitrogen and heated to 30 ° C. As soon as this temperature is reached, an air-free solution of 2.97 parts of sodium thiosulfate in 42 parts of water is started to be added dropwise. The addition takes place within 8 hours, the temperature rising to 50 ° C. A fine polymer-containing dispersion is obtained which can be diluted well with water.

Example 4

500.0 parts of the preparation obtained according to Example 1 are mixed with 10 parts of White Spirit (CO and 10 parts of emulsifier (B2) with stirring. Then the mixture is evacuated to 26 mbar and the temperature is raised from room temperature to 40 ° C., about 200 Parts of water are regularly distilled off using a water separator, resulting in a fine, stable, polymer-containing dispersion that can be easily diluted with water.

Example 5

The procedure is as described in Example 1 and 10% (based on the weight of the preparation obtained according to Example 1) of the 20% preparation according to Example 3.1 from French Patent 1,583,363 are added to the preparation obtained, with stirring, which also results in a stable W / O emulsion received.

Example 6

Part 1: Dispersion (1)

454.00 parts of acrylamide, 353.00 parts of a 75% aqueous solution of methacryloyloxyethyltrimethylam-5 monium chloride and 800.00 parts of water are loaded into a sulfonation flask and stirred. After the acrylamide has dissolved, 1.43 parts of ethylenediamine-tetraacetic acid disodium salt and 0.72 parts of iron (III) sulfate are added to the reaction solution and the pH is adjusted by adding about 0.10 parts of 30 % sodium hydroxide solution to 3.0. A solution of 143 parts of emulsifier (DO in 440 parts of white spirit (C2)) is then poured into the monomer solution with vigorous stirring. A milky water-in-oil emulsion is formed, which is then 5 times to an i5 pressure of Evacuated 26 mbar and relieved of nitrogen in each case. A strong nitrogen stream is then passed through the air-free emulsion at high stirring speed. Then 0.67 parts of tert-butyl hydroperoxide are added to the cold reaction mixture and the mixture is heated to 20 3 5 ° As soon as this temperature has been reached, 50 parts of a solution of 2.70 parts of sodium thiosulfate in 50.00 parts of water of the monomer emulsion are added dropwise within 5 hours 36-38 ° C. Then the mixture is left to react for a further 2 hours at 35 ° and then cooled to room temperature, the nitrogen supply r parked and unloaded.

30 Part 2: Addition of (b \)

200 parts of the dispersion (1) prepared in accordance with part 1 are mixed with 20 parts of white spirit (C2) and 20 parts of a 30% mineral oil solution of the petroium sulfonate (B0 in the form of the calcium salt however, despite the high viscosity, it can be quickly diluted with water when added to water (eg 4 parts product to 396 parts water).

Part 3: Production of (b /)

4o The petroleum sulfonate (B0 in the form of the calcium salt is prepared by treating a 20% aqueous emulsion of (BO (sodium salt) with an excess of CaCl2, filtering off the precipitated (B0 calcium salt, washing with water and under vacuum at 60-70 ° dries.

45

Example 7

200 parts of dispersion (1) according to Example 6 (part 1) are mixed with 25 parts of a solution of 10 parts of a paraffin sulfonate (B3) in the form of the calcium salt in 80 parts of white spi-50 rit (C2) and 30 parts of mineral oil (C3 ) offset. The mixture obtained can be diluted very well with water. The calcium salt of the surfactant (B3) is prepared analogously to that described in Example 6, Part 3, with the corresponding amount (B3) being used instead of B.

55

Example 8

200 parts of the dispersion (1) according to Example 6 (Part 1) are mixed with 30 parts of a solution of the following percentage composition:

60 14.3% petroleum sulfonate sodium salt (B2)

57.1% mineral oil (C3)

28.6% of a 50% solution of triisobutyl phosphate (F0 in isobutanol added. A viscous product is obtained which can be easily diluted at 65 when added to water.

Example 9

2210 parts of the polymer

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Saturated emulsion are, after the addition of 330 parts of mineral oil (C3) and 330 parts of petrolatum (C4), evacuated to 26 mbar with stirring and heated to 40 ° C within about 6 hours, with 860 parts of water being regularly distilled off using a water separator. A little oil distills together with water, which collects in the water separator at the surface of the water and is regularly returned to the reaction vessel. A very fine, stable, slightly viscous dispersion is obtained which can be diluted with water approximately as well as the product according to Example 1.

Example 10

A dispersion inertized with nitrogen consisting of

960.0 parts water 816.6 parts acrylamide

1128.0 parts of a 75% aqueous methacryloyloxy-ethyltrimethylammonium chloride solution 2.9 parts of ethylenediamine-tetraacetic acid-di-sodium salt

1.5 parts iron (III) sulfate 9.1 parts calcium chloride 48.0 parts emulsifier Bi 60.0 parts emulsifier D,

60.0 parts of emulsifier D2 960.0 parts of white spirit (CO, which was adjusted to pH 3.0 with a little sulfuric acid, are first added to initiate the polymerization reaction, 1.2 parts of tert-butyl hydroperoxide. Then one of air is added dropwise freed solution of 6.5 parts of sodium thiosulfate in

20.0 parts of water started. The addition takes place within 8 hours, the temperature rising to about 48 ° C. despite cooling. After the thiosulphate has been added, 165.7 parts of mineral oil (C3) and 27.7 parts of emulsifier (D3) are added to the polymer-containing emulsion and then distilled under vacuum (20-26 mbar) and at an internal temperature of max. 50 ° C using a water separator approx 1186 g of water. A very fine, thin dispersion is obtained which, after the water has been distilled off, is mixed with 157.5 parts of olive oil (C5) and 157.5 parts of 2-ethylhexanol (F2). The dispersion containing olive oil and 2-ethylhexanol can be instantly diluted in water.

Example 11

The procedure is exactly the same as in Example 10, but the 2-ethylhexanol (F2) is replaced by triisobutyl phosphate (Fj).

Example 12

The procedure is exactly the same as in Example 10, but the 2-ethylhexanol (F2) is replaced by tributoxyethyl phosphate (F3).

Example 13

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

Example 14

43.5 parts of emulsifier (B |) are mixed with 834.0 parts of water, producing a very fine, opalescent emulsion. Now 8.2 parts of calcium chloride are added to form the calcium salt of (Bi). 557.0 parts of acrylamide, 216.0 parts of a 75% strength aqueous methacryloyloxyethyltrimethylammo-

nium chloride solution, 1.4 parts of ethylenediamine-tetraacetic acid di-sodium salt and 0.7 part of iron (III) sulfate are added, a cloudy solution being formed. 400.0 parts of isoparaffinic solvent (C6), 40.0 parts of mineral oil (C3), 100.0 parts of emulsifier (Di) and 13.0 parts of emulsifier (B2) are then added. A water-in-oil emulsion is formed, which is inertized with nitrogen. Then 0.7 part of tert-butyl hydroperoxide and then 6.0 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.

Example 15

15 The following changes are carried out as in Example 14:

- 709.0 parts of water are used instead of 834.0 parts

- 183.3 parts of acrylamide are used instead of 20 of 557.0 parts

- 714.0 parts of 75% methacryloyloxyethyl trimethylammonium chloride solution are used instead of 216.0 parts

- The temperature rises to approx. 43 ° C under adiabatic conditions

- After the polymerization, 33 parts of Pluro-nic L101 (F5) and 165 parts of fatty acid methyl ester mixture (C7) are added.

30 Example 16

The following changes are carried out as in Example 14:

- 160.0 parts of mineral oil (C8) are used instead of 40.0 parts of mineral oil (C3)

35 - the temperature is kept between 35 and 40 ° C.

Example 17

43.5 parts of emulsifier (B0 are mixed with 800.0 parts of water, giving a fine, opalescent emulsion. 40 parts of calcium chloride, 363.0 parts of acrylamide, 124.0 parts of dial -lylamine, 353.0 parts of a 75% methacryloyloxyethyltrimethylammonium chloride solution, 131.0 parts of hydrochloric acid (34%) to adjust the pH to 3.0, 1.4 parts of 45 ethylenediamine-tetraacetic acid di-sodium salt and 0 , 7 parts of iron (III) sulfate are added to form a homogeneous monomer solution, to which 400.0 parts of white spirit (CO 40.0 parts of mineral oil (C3) and 100.0 parts of emulsifier (DO) are then added a fine emulsion which is erted with nitrogen in 50. Then 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 to start the polymerization reaction. An exothermic reaction occurs, the temperature below adia-55 batis conditions up to 65 ° C.

Example 18

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

- Instead of 52.0 parts of emulsifier (B :), 29.0 parts are now used;

- Instead of 80.0 parts of emulsifier (DO, 49.0 parts of emulsifier (D3) and 65.0 parts of emulsifier (D4) are used.

65

Example 19

43.5 parts of emulsifier (B0 are mixed with 800.0 parts of water, giving a fine, opalescent emulsion

660 015

14

stands. Now 8.2 parts calcium chloride and then 454.0 parts acrylamide, 353.0 parts 75% aqueous methacryloyloxyethyltrimethylammonium chloride solution, 1.4 parts ethylenediaminetetraacetic acid di-sodium salt and 0.7 parts iron (III) -sulfate added. The solution obtained is then mixed with 400 parts of white spirit (Q), 40.0 parts of mineral oil (C3), 100.0 parts of emulsifier (D () and 54.0 parts of emulsifier (B2). A water-in is formed Oil emulsion which is rendered inert with nitrogen, 0.7 parts of tert-butyl hydroperoxide and then 45.0 parts of a solution of 2.7 parts of sodium thiosulfate in 50 parts of water are then added dropwise to initiate the polymerization reaction exothermic reaction, the temperature rising to 90 ° C. within about 90 minutes.

Example 20

43.5 parts of emulsifier (Bj) are mixed with 600.0 parts of water. 8.2 parts of calcium chloride, 454.0 parts of acrylamide, 1.4 parts of ethylenediamine-tetraacetic acid di-sodium salt, 0.7 part of iron (III) sulfate, 400.0 parts of white spirit ( Q), 40.0 parts of mineral oil (C3), 100.0 parts of emulsifier (D]) and 13.0 parts of emulsifier (B2) were added. A water-in-oil emulsion is formed, which is then rendered inert with nitrogen and mixed with 0.7 part of tert-butyl hydroperoxide and with 1.0 part of a solution of 2.7 parts of sodium thiosulfate in 50.0 parts of water. The exothermic polymerization reaction occurs immediately, the temperature being kept at about 60 ° C. Shortly before the exothermic reaction subsided, an air-free solution of 265.0 parts of methacryloylethyltrimethylammonium chloride in 288.0 parts of water began to be added dropwise, the temperature rising again and 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.).

Example 21

The following changes are carried out as in Example 15:

- 11.00 parts of emulsifier (Bj) are used instead of 43.50 parts

- 25.00 parts of emulsifier (D |) are used instead of 100.00 parts

- 3.25 parts of emulsifier (B2) are used instead of 13.00 parts

- After the polymerization, (F5) and (C7) are not added.

Example 22

The following changes are carried out as in Example 16:

- 21.75 parts of emulsifier (B,) are used instead of 43.50 parts

- 50.00 parts of emulsifier (Dj) are used instead of 100.00 parts

- 6.50 parts of emulsifier (B2) are used instead of 13.00 parts.

Emulsifiers used

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

Emulsifier (B2): 60% solution of a petroleum sulfonate (monosulfonate) in the form of the sodium salt with a molecular weight of 480 in mineral oil.

Emulsifier (B3): Secondary n-alkanesulfonates produced by sulfoxidation of paraffins in the form of the sodium salts, in which the alkane radical has on average the following composition:

Ci3-C, 5 = 58% 5 C16-C17 = 39%

> C17 <3%

<C13 <1%

Emulsifier (D,): Ci2H25- (OCH2CH2) 2-OH HLB = 6.5 Emulsifier (D2): CI8H35- (OCH2-CH2h-OH HLB = 6.5 10 Emulsifier (D3): Sorbitan monooleate HLB = 4.0

Emulsifier (D4): Mixture of C17H33CO (OCH2CH2) 6i5-0-CO-C17H33 and Ci7H33CO (OCH2CH2) 6 5-OH in a molar ratio of 1: 1, average HLB = 7.0

15 .. •

Oils used

White spirit (Q): aromatic-free terpenaline, boiling range 193-247 ° C, average molecular weight 173.

White spirit (C2): low aromatic terpenaline, Siedebe-20 range 190-250 ° C, average molecular weight 180, aromatic content 0.5%.

Mineral oil (C3): partially unsaturated mineral oil with the following specifications:

Density 0.85-0.95 25 'aniline point 70-80 ° C iodine number 20-30.

Petrolatum (C4): Petrolatum with solidification point = 50-85 ° C and cone penetration at 25 ° C = 160-180 olive oil (C5):

30 Isoparaffin (C6): Isoparaffinic oil with:

Boiling range 210-260 ° C aniline point 88 ° C isoparaffin content 80%

Density 0.78

35 Fatty acid methyl ester mixture (C7): methyl esters of C12 to C20 fatty acids with the following specifications:

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

Mineral oil (C8): hydrocarbon mixture with the following specifications:

Density 0.85-0.95 45 aniline point 95 ° C

Viscosity (20 ° C) 30 cp

Solvents used

(Fj) triisobutyl phosphate (50% solution in isobutanol) 50 (F2) 2-ethylhexanol

(F3) Tri-butoxyethyl phosphate (F4) 2,4,7,9-tetramethyl-5-decyn-4,7-diol (F5) Pluronic L101: ethylene oxide propylene oxide co-polymer with molecular weight 3610 and 10 wt. -% ethy-55 lenoxide units.

Dilution example I A mixer is used in which a rice chamber and 5 mixing chambers are arranged horizontally and 60 represent a total of a cylinder whose axis is horizontal; the inner diameter of the individual chambers is 110 mm and the inner volume of each chamber is 2.5-10-3 m3. The inside diameter of the tube for the water supply of the connecting hoses between 65 and 65 see rice chamber and mixing chamber and between the mixing chambers and the line for the removal of the diluted product are the same. The connecting hoses between the chambers and their nozzles have one

15

660 015

Inner diameter of 15 mm; the length of the hoses is 40 cm each.

In the tearing chamber of the mixer through a check valve provided with a polymer nozzle with an opening of 2 mm in diameter, 10 (1 / h) of the preparation according to Example 1 (polymer emulsion) in pulses, with a frequency of 50 sec-1 and through a water nozzle an opening of 15 mm diameter pumped 2000 (1 / h) water. The speed of the water at the nozzle opening is 3.2 m / s (= Re 47 000) and it flows around the entire polymer nozzle.

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

Dilution example II

The procedure is as described in Example I, but a mixer according to Fig. 2 (and 2a) is used, in which the polymer nozzle has 6 openings of 1 mm in diameter and pumps 5 (1 / h) polymer emulsion according to Example 1 into the mixer. The diluted product emerging from the mixer is a ready-to-use aqueous solution of the polymer and is ready for use in papermaking.

Application example A

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

100 parts bleached sulfite pulp 20 parts kaolin 3 parts resin glue 2 parts aluminum sulfate

Before the sheet is formed on the Rapid Köthen sheet former, 250 ml of test substance with 5 resp. 10, 15 and 20 ml of a 0.0125% aqueous dilution of the product according to Example 1 and mixed with 750 ml of dilution water. After a stirring time of 5 seconds at 250 revolutions / minute, the substance / water mixture is transferred into the filling chamber of the sheet former (Rapid-Köthen system), 3 liters of water being placed in the filling chamber. After a holding time of 20 seconds, the sheet is formed by actuating the suction valve. After the test sheets have been dried and conditioned, they are incinerated.

The ash content is related to the filler used and expressed in% retention. The result is summarized in the following table; the values given for% ash and% retention are each 5 mean values from two determinations.

Amount added in ml 0.0125% solution

5

10 15

i5 20

Zero value

Flocculant concentration * in% (based on dry paper stock)

0.0125 0.025 0.0375 0.05

%

ash

13.31 14.34 14.66 14.73 8.51

%

Retention

79.9 86.0

88.0 88.4

51.1

"(Polymer emulsion)

20th

Application example B 200 parts of a digested sludge suspension with 5% dry matter content are initially mixed with w parts of a 0.23% aqueous dilution of the preparation prepared according to Example 1 and then for 10 seconds using a «Triton» stirrer at one speed of 1000 revolutions / minute. Then the sludge suspension is immediately filtered on a cloth filter and the mean volume of the filtrate is determined after 30, 60, 90, 120 and 180 seconds.

30th

w Average volume

0 1.5 parts by volume

13 15.3 parts by volume

35 15 40.4 parts by volume

17 49.1 parts by volume

19 81.9V volume parts

The products of Examples 2-22 can be used in an analogous manner to that described in Application Examples A "o and B.

1 sheet of drawings

Claims (13)

660 015 1. Water-dilutable, polymer and surfactant-containing preparations, characterized in that they contain a) a hydrophilic, cationic polymer and b) an anionic surfactant, which is a sulfonated hydrocarbon, the molar proportion of anionic surfactant b ) is not greater than the molar proportion of cationic monomer units of the polymer a) and the cation of the polymer and the anion of the anionic surfactant can be combined to form the salt. 2. Preparations according to claim 1, characterized in that part of the cationic groups of a) is in a salt form in which the anion is that of the anionic surfactant b). 2nd PATENT CLAIMS 3. Preparations according to claim 1, characterized in that they contain as further components c) at least one water-miscible oil in which the polymer is not soluble, but is finely divided therein and, if appropriate, d) a lipophilic or oil-soluble, non-ionogenic Surfactant and / or e) water and optionally f) an oil-miscible, sparingly water-soluble and non-self-dispersible, polar solvent which alone has no emulsifier properties, but which lowers the interfacial tension water / oil. 4. Preparations according to claim 3, characterized in that c) is a mixture of oils C]) and c2) which is selected such that the O / W-EHLB value of C |) is greater than the O / W -EHLB value of the mixture q) + c2). 5. Hydrophilic cationic polymers, wherein a part of the cationic group is in a salt form as defined in claim 2. 6. A process for the preparation of preparations according to claim 1, characterized in that the anionic surfactant b), before, during and / or after the polymerization, is combined with the polymer a) or with the corresponding monomers. 7. The method according to claim 6, characterized in that c) at least one water-immiscible oil in which the polymer is not soluble, but is finely divided therein, and optionally d) a lipophilic or oil-soluble, non-ionic surfactant and / or e) water and optionally f) an oil-miscible, sparingly water-soluble and self-dispersible, polar solvent which alone has no emulsifier properties but reduces the interfacial tension water / oil. 8. vinyl monomer salts, wherein the cation is that of a cationic vinyl monomer and the anion is that of an anionic surfactant, the anionic surfactant being a hydrocarbon sulfonate, as intermediates in the process according to claim 6. 9. W / O emulsions containing monomer salts according to claim 8, wherein the oil is an oil c) as defined in claim 7, as intermediates in the process according to claim 7. 10. W / O emulsions according to claim 9, which also contain a non-ionic surfactant d) as defined in claim 7. 11. Use of the preparations according to claims 1-3 as a flocculant. 12. Use according to claim 11 for the production of paper. 13. Use according to claim 11 for wastewater treatment. Hydrophilic, i.e. Water-soluble or dispersible, cationic polymers are increasingly being used in industry today, e.g. as a flocculant, and rapid dispersibility or dilution with water of the xo preparations containing such polymers is of great importance. It has been found that preparations can be produced which, in addition to an excess of cationic, water-soluble polymer, contain an anionic surfactant optionally in a form bound with salt formation, i5 the polymers being finely distributed in the preparation and the preparations being readily dispersible in water or good with water are dilutable.