DE2552014A1 - MIXTURES BASED ON POLYACRYLAMIDES WITH WATER-SOLUBLE, RESINY AMINO CONDENSATION PRODUCTS - Google Patents

Description

BASF Aktiengesellschaft;

Our reference: O ₀ Z ₀ 31 686 Ks / MK 6700 Ludwigshafen, November 18th ". 1975

Mixtures based on polyacrylamides with water-soluble, resinous amino condensation products

The invention relates to mixtures based on water-soluble, neutral or cationic polymers of acrylamide and water-soluble resinous amino condensation products »

Polyacrylamides, which are commercially available as powders, are most commonly used in the form of dilute aqueous solutions »Man must therefore dissolve the powder in water. However, this often occurs Difficulties arise because the polymer easily clumps when it is added to water. It is also known to use dilute aqueous polyacrylamide solutions by producing a water-in-oil dispersion containing the polyacrylamide instead of the solid polymer contains in the dispersed aqueous phase, enters water ο The acrylamide polymer dissolves after phase reversal the water-in-oil dispersion very quickly and without clumping »

From DT-PS 1 89 173 it is known acrylamide polymers containing water-in-oil dispersions by adding a water-in-oil emulsion of an aqueous solution of acrylamide, the optionally contains other water-soluble ethylenically unsaturated monomers, polymerized in a hydrophobic, organic dispersion medium in the presence of a polymerization initiator. As a hydrophobic organic dispersion medium that forms the continuous phase of the water-in-oil dispersions Hydrocarbons and perchlorethylene recommended »

Water-in-oil dispersions of polyacrylamides Z are ₀ B ₀ as flocculants to clarify aqueous systems in paper production, in the treatment of municipal and industrial waste water, as a dispersant for protective colloids for drilling muds and as an aid in the secondary recovery of petroleum in Used in flood waters »

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Resin-like amino condensation products are, for example, polyalkyleneimines, Alkylenepolyamine-epichlorohydrin resins or reaction products of alkylenimines with aminopolyamides. These products are commercially available as 20 to 30% aqueous solutions. The viscosities of the commercial solutions are in the range from 100 to 10,000 mPa.s. The amino condensation products are in usually before use, e.g. "as a drainage and retention aid, further diluted with water

Since 5 # aqueous polyacrylamide solutions already have such a have a high viscosity that they can no longer or only poorly pumped, aqueous polyacrylamide solutions and aqueous Solutions of resinous amino condensation products are not mixed with one another at will. There is also the risk that due to polymer incompatibilities between polyacrylamides and resinous amino condensation products such as polyalkyleneimines or alkylenepolyamine epichlorohydrin resins, mixtures of aqueous solutions of these polymers "

The object of the invention is to provide a mixture of polyacrylamides and to show resin-like amino condensation products, even with a predominant polyacrylamide content and relatively high solids content is resistant and pumpable

The invention relates to mixtures based on water-soluble neutral and / or cationic polymers of acrylamides and water-soluble resinous Amino-condensation products, which are characterized ₉ that they are present in the discontinuous phase of a water-in-oil dispersion = The polymer blends can thereby 95 to 40% by weight of a neutral or cationic acrylamide polymer and 5 to 60% by weight of a water-soluble resinous amino-condensation product contain Gewo # on «

Dilute aqueous solutions of the mixtures according to the invention surprisingly show a higher effectiveness when used as a flocculant, sedimentation aid, drainage

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and retention aids than the individual polymeric products the mixture and also as combinations of aqueous solutions of the above Polymers.

The aqueous phase of the dispersion is dispersed in a hydrophobic organic dispersion medium. The hydrophobic organic dispersion medium used can be, for example, those liquids which are described in DT-PS 1 089 173, such as aromatic liquid hydrocarbons, Z ₀ B ₀ toluene and xylene, Perchlorethylene and aliphatic liquid hydrocarbons such as paraffin oils. In general, saturated hydrocarbons whose boiling points are in the range of 120 to about 35O ⁰ C. Pure hydrocarbons and also mixtures of two or more hydrocarbons can be used. Preferably, a mixture of saturated hydrocarbons containing up to 20 wt.% Naphthenes contains. The saturated hydrocarbons are n- and i-paraffins. The boiling limits of the mixture are 192 to 25 ² I ⁰ C (determined according to ASTM D-IO78 / 86).

The stability of the dispersions against coagulation and sedimentation can to ensure they oil-water-in-emulsifiers known, for example sorbitan, sorbitan GIycerinester whose acid component is ₁ ^ C - contain up Cp _O carboxylic acids derived and CetyIstearylnatriumphthalat.

The emulsifiers suitable for this purpose have an HLB value of at most 8 and the dispersion contains 0.1 to 30, preferably 1 to 10, wt. #. The HLB value is understood to mean the hydrophilic-lipophilic balance of the emulsifier, ie the balance of the size and strength of the hydrophilic and lipophilic groups of the emulsifier. A definition of this term can be found, for example, in "Das Atlas HLB-System", Atlas Chemie GmbH, EC 10 G July 1971 and in Classification of Surface Active Agents by "HLB", W ₀ C ₀ Griffin , Journal of the Society of Cosmetic Chemist , P. 311 (1950).

In addition, the water-in-oil dispersions according to the invention, to ensure that they can be thinned directly with water more quickly.

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most, still 0.5 to 5 wt. % Of wetting agents with an HLB value of over 10 contain. These are essentially hydrophilic, water-soluble products such as ethoxylated alkylphenols, dialkyl esters of sodium sulfosuccinates in which the alkyl group has at least 3 carbon atoms, soaps which are derived from fatty acids with 10 to 22 carbon atoms, and alkali salts of alkyl or alkenyl sulfates 10 to 26 carbon atoms. Ethoxylated nonylphenols with a degree of ethoxylation of 6 to 20, ethoxylated nonylphenol-formaldehyde resins with a degree of ethoxylation of 6 to 20, dioctyl esters of sodium sulfosuccinates and octylphenol polyathoxyethanol are preferably used

The production of water-in-oil dispersions of homo- and copolymers of the acrylamide can be done in known ways »For example, the production of such dispersions is described in DT-PS 1 Ο89 173, BE-PS 814 401, DT-OS 2 226 143 and DT-OS 2 344 018 described.

The homo- or in the dispersions according to the invention Acrylamide copolymers are water-soluble. The molecular weights are between 100,000 and 25,000,000, preferably between 1,000,000 and 25,000,000. As comonomers in the Copolymers of acrylamide in question are water-soluble and have an ethylenically unsaturated double bond, It can be non-ionic and neutralized or quaternized be basic compounds, for example esters of amino alcohols of acrylic acid or methacrylic acid or amides of Dialkylaminoalkylamines of acrylic acid or methacrylic acid.

Suitable cationic monomers are also vinylimidazole and vinyl pyridine. The following monomers deserve special mention: Dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, Dibutylaminoethyl methacrylate, dimethylaminomethyl acrylate and methacrylate and diethylaminopropyl acrylate and methacrylate.

Further suitable ethylenically unsaturated, water-soluble monomers are disclosed in US Pat. Nos. 3,418,237 and 3,259,570

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and 3,171,805. The acrylamide polymers contain up to 90% by weight, preferably 2 to 50% by weight, of a comonomer or a mixture of several comonomers.

Resinous amino condensation products are also known and are commercially available. These include, for example, water-soluble Polymers of alkylenimines, such as polyethylenimine, water-soluble polyalkylene polyamines, for example by condensation of alkylene dihalides with polyalkylene polyamines or halohydrins are produced with polyalkylene polyamines. This class of condensation products also includes the reaction products of alkylene dihalides or halohydrins with ammonia “The preferred halohydrin is epichlorohydrin used »Other resinous amino condensation products are, for example, the water-soluble condensates made from polyamides and Epichlorhydridn, which are known from DT-PS 1 177 824, and condensation products, which are also polymerized in caprolactam contain »Under the definition resinous amino condensation products also fall basic polyamidoamines, which are known in Way by amidation of dicarboxylic acids and optionally aminocarboxylic acids and / or their lactams with 0.8 to 1.5 mol of di- and / or polyamines are obtained as well as those products that additionally contain alkyleneimines, preferably ethyleneimine grafted on »Products of this type are for example in the DT-OS 1 802 435 describes “Further suitable resinous amino condensation products are obtained by reacting 1 mole of a polyether with 2 moles of ethylene chlorohydrin and the condensation product if necessary grafted with ethylene imine “With advantage those amino condensation products can also be used, which in place of grafted ethyleneimine with a Polyether dichlorohydrin were implemented »Likewise, those Reaction products are used, the reaction of a Polyamidoamine, which is optionally grafted with ethyleneimine, with polyalkylene oxide derivatives are obtained, which at the terminal OH groups with at least equivalent amounts of epichlorohydrin are implemented.

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The resinous amino condensation products are usually commercially available in the form of $ 20 to $ 50 aqueous solutions. The viscosity of the 20 # aqueous solution of the amine condensation products is 100 to 2,000 mPa _s s.

The water-in-oil dispersions according to the invention are prepared in such a way that a 20 to 50% aqueous solution of a resinous amino condensation product is added to a water-in-oil dispersion of a homo- or copolymer of acrylamide and the aqueous solution emulsifies _o The aqueous solution of the amino condensation product is then emulsified in the water-in-oil dispersion of the acrylamide polymer using a homogenizer, for example Components of the mixture is not critical. With a high ratio of resinous amino condensation product to acrylic acid polymer, the amount of outer phase of the water-in-oil dispersion is expediently increased to such an amount that pumpable dispersions are still obtained.

The water-in-oil dispersions according to the invention are stable, contain a high proportion of polymers and are very easy to dilute with water, especially if they contain a wetting agent or if a wetting agent with an HLB value of> 8 is added to the dilution water ₀

The mixtures according to the invention of water-in-oil dispersions can be used, for example, as flocculants for clarifying aqueous systems, in paper manufacture, in the treatment of waste water, as a dispersant and protective colloid for drilling mud and used as an aid in the secondary extraction of petroleum in flood waters »In all cases you need a lot dilute solutions, so that the dispersions prepared according to the invention are diluted with water »

Water-in-oil dispersions are mixtures of high molecular weight homo- or copolymers of acrylamide with resinous ones Amino condensation products are liquid and still contain more than 10% strength

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Shape (based on the total polymer content) can be produced in a pumpable manner without disruptive incompatibilities between the individual components occur in the polymer mixture »

Furthermore, these mixtures have a, based on the polymer content, better effectiveness as a flocculant, sedimentation, drainage and retention agent than any of the individual polymer components.

The following examples illustrate the invention "The parts specified in the examples are parts by weight and percentages relate to the weight of the materials» The K values of the polymers were determined according H ₀ Fikentscher, Cellulose Chemie 1 £, 58 to 64 and 71 bis 74 (1932), 0.1 % in 5 # aqueous NaCl solution be:
at means K = k. 10 "

measured aqueous NaCl solution at a temperature of 25 ° C; daDie Viscosities were measured in a Brookfield viscometer at 20 rpm »

The following water-soluble resinous amino condensation products were used in the examples 1

Solution A:

20 $ aqueous solution of a condensation product of a polyamidoamine (from diethylenediamine, triethylenetetramine and adipic acid) and ethyleneimine, which is crosslinked with epichlorohydrin and was prepared according to Example 2 of DT-OS 1 802 435, viscosity of the solution at 20 ⁰ C 800 mPa .s, ρH value set to 5 with sulfuric acid »

Solution Bs

20 ^ aqueous solution of a reaction product of a polyamidoamine grafted with ethyleneimine (from diethylenetriamine and adipic acid) and a 40-fold oxyethylated ethylene glycol in a weight ratio of 3: 2 at 20 ⁰ C 700 mPa _o s, pH adjusted to 5 with sulfuric acid.

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Solution C:

30 # aqueous solution of a polyethyleneimine; Viscosity of the 20 # aqueous solution

adjusted to pH 5.

20 # aqueous solution at 20 ⁰ C 2,500 mPa.s, with sulfuric acid

Solution D;

18 # aqueous solution of a reaction product of a polyamidoamine (from diethylenetriamine and adipic acid) and a 45-fold oxethylated ethylene glycol in a weight ratio of 3: 2 which has been completely reacted at the OH groups with epichlorohydrin. Viscosity of 20 # aqueous solution at 20 ⁰ C 900 _o mPa s, adjusted with sulfuric acid to pH. 5

Solution E;

20% aqueous solution of a reaction product from a PoIyamidoamin (from adipic acid and diethylenetriamine) and epichlorohydrin according to Example 1 of the DT-PS 1177824 "viscosity of the% aqueous solution at 20 ⁰ C 250 mPa.s, with sulfuric acid to pH 5 set.

example 1

The 20% aqueous solution A is emulsified into a 25 # water-in-oil dispersion of a copolymer of acrylamide with the sulfate of diethylaminoethyl acrylate using an Ultraturrax Example 3 of DT-OS 22 26 143 produced. However, the detailed composition of the above-mentioned 25 # cationic polyacrylamide water-in-oil dispersion is as follows:

25 parts of a copolymer of 0.846 mol of acrylamide with 0.153 of the sulfate of diethylaminoethyl acrylate, K value

45 parts of water

24 parts of mixture of 84% saturated aliphatic hydrocarbons and 16% naphthenic hydrocarbons (boiling range of the mixture 192-254 ⁰ C) 3 parts of sorbitan monooleate

1 part ethoxylated nonylphenol (degree of ethoxylation 8-12)

2 parts ethoxylated castor oil

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In Examples 1 to 5, this water-in-oil dispersion referred to as dispersion A (it does not contain any resinous amino condensation product).

Up to a mixing ratio of 1 part of dispersion A to 0 to 1.1 parts of 20 % aqueous solution A, the aqueous solution A can be emulsified into the continuous organic phase of dispersion A without diluting the continuous organic phase, the proportion by weight of the discontinuous inner phase the dispersion up to about 80 wt%. increases.

With a higher proportion of solution A in the total mixture, the proportion of the outer phase by adding so many parts of a mixture

2k parts mixture of Sk% saturated aliphatic hydrocarbons and 16 % naphthenic hydrocarbons (boiling range of the mixture 192 to 245 ° C) 3 parts sorbitan monooleate

1 part ethoxylated nonylphenol (degree of ethoxylation 8-12)

2 parts ethoxylated castor oil

increased so that the internal phase of the dispersion in each case remains below 80 wt "%"

The dispersion A is intensively mixed with the resinous amino condensation products (solutions A to E) described above, so that stable water-in-oil dispersions are present. The composition of the dispersions thus obtained, the side by side the cationic polyacrylamide and the cationic Amino condensates contained in the discontinuous phase is given in Table 1 »

Stable mixed dispersions are obtained in which, as can be seen in Examples 1.1.1 to 1.1.3 and Tables 2 to 5 is, a clear synergistic effect in the effect of the combination of both polymers when used as retention and Drainage aid occurs in paper manufacture and in the plocking of municipal sewage sludge.

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Example 1.1.3 and Table H also show that the effect of the aqueous dilute mixed solution prepared from the water-in-oil combination dispersions prepared as described above is significantly better than the effect of a combination of dilute aqueous polyacrylamide solutions prepared separately and the Solution of a condensation product of a polyamidoamine and ethyleneimine, which is crosslinked with epichlorohydrin (prepared from dispersion A and solution A).

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Dis Polyacrylic Wt.% Polyacrylic resinous. Weight% resin » Ratio Poly Weight % interior by amide type amid in the Dis Amino art. Amino acrylamide Phase in the sion persion condensate condensate too resin Dispersion in the dis art. Amino persion condensate in the dis persion A. Cationi 25.0 100/0 70.0 B. cal poly
acrylamide 2t J 2 5.3 80/20 75.1 C. Copolymer 19.1 8.2 70/30 77.6 D. sat off
$ 0.846 moles 16.9 Solution a 6.8 60/40 80.1 THERE Acrylamide 10.7 16.1 40/60 76.6 DB With 0.153
Mol # des 5.1 20.5 20/80 73.5 E. Sulfate des 20.9 5.2 80/20 75.4 P. Diethy! Ami
noether! - 16.5 11.0 60/40 80.6 G acrylate 10.3 Solution b 15.5 40/60 77.5 GA 4.9 19.6 20/80 74.7 H 19.9 " 4.9 80/20 76.6 I. 14.3 9.5 60/40 79.0 J 8.8 Solution C 13.2 4o / 6o 78.3 K 4.2 16.8 20/80 79.0 L. 19.0 4.8 80/20 80.0 M. 12.8 08 ^ 5 60/40 79.0 N 7.7 Solution E 11.5 40/60 79.0 0 3.4 13.8 20/80 78.0 P. 18.8 4.7 80/20 78.2 Q 12.4 8.3 60/40 7 * 9.3 R. 7.2 Solution D 10.8 40/60 77.6 S. 3.2 12.7 20/80 76.3 T Acrylamide 25.0 - - 100/0 70.0 U i.e. omopoly-
merisat 22.0 2.4 90/10 74.5 V 19.0 4.8 80/20 77.9 W. 15.5 Solution a 6.6 70/50 77.2 X 12.3 8.2 60/40 76.1 Y 7.4 11.1 40/60 76.4 Z 3.3 13.2 20/80 75.3

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1.1 Effect of the dispersions in papermaking

1.1.1 retention effect

A fabric made of 80 % was bleached. Sulphite pulp and 20 % China Clay Xl prepared with an initial grind of 35 ° SR. From this material, sheets with a sheet weight of about 70 g / m 2 were produced in a laboratory sheet former once in the presence of 1.5 % alum (pH 4.8) and once in the presence of 0.5% alum (pH 6.0) 0.015% by weight of solid polymer substance (pure polymers compared to the polymer mixtures according to the invention) were used as a 0.1 % strength aqueous solution. The 0.1% strength aqueous polymer solution was prepared on the basis of the water-in-oil dispersions according to the invention.

The ash content of the leaves thus prepared was determined. Table 2 shows the superior synergistic effect. Only at an amount of 70 % solution A is the level of the pure cationic polyacrylamide reached again, although the pure solution A has a significantly weaker effect than the pure cationic polyacrylamide.

Table 2: Retention effect [polymer solid used: 0.015% by weight]

Product % ash in the leaf

709821 / 1.4 % alum 0.5 % alum; pH 4.8 pH 6.0 Comparative examples: without addition 4.7 4.9 Dispersion A 12.9 12.8 Solution a 7.4 7.4 Example gladly. Invention? Dispersion B 14.1 14.0 Dispersion C 14.0 13.9 Dispersion D 13.1 13.0 Dispersion DA 11.9 11.2 0852

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1.1.2 Acceleration of drainage

A stock of 100 # waste paper with an initial grind of 59 ° SR is prepared. At this fabric the Mahlgradbeeinflussung was measured by the addition of polymer at 0.04 wt _o # polymer solids in a Schopper-Riegler freeness testing device. In this case, 0.04% by weight of solid polymer substance (pure polymers in comparison with the polymer mixtures according to the invention) was used as a 0.1 # aqueous solution. The 0.1 # aqueous polymer solution was prepared on the basis of the water-in-oil dispersions according to the invention

Table 3: Reduction of the degree of grinding

[Polymer solid employed: 0.04 % J

product Grind ⁰ SR Alum; 1.5 % alum; without , 0 pH 4.8 pH 7 Comparative examples: 59 without addition 54 46 Dispersion A 42 45 Solution a 35 Example according to the invention: 39 Dispersion B 30th 41 Dispersion C 28 37 Dispersion D 25th 37 Dispersion DA 27

Table 3 shows the superior synergistic effect. In the entire range studied the combination of the polymers is in the form of their water-in-oil dispersions, a compared with the pure blend components significantly stronger Mahlgradsenkung, which amounts to 1O ⁰ SR.

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1.1.3 Comparison of the effect of a dilute aqueous solution obtained from the mixed dispersion according to the invention (cf. Table 1) was prepared, with that of an aqueous solution prepared by mixing a dilute aqueous solution of the corresponding polyacrylamide with a dilute solution A was prepared.

The retention effect in papermaking was compared for both cases. A fabric made of 80 % bleached. Sulphite pulp and 20 % China Clay Xl with an initial degree of grinding of 35 ° SR. From this material, sheets with a sheet weight of approx. 70 g / m ² were produced in a laboratory sheet former in the presence of 1.5% alum (pH 4.8) 0.015 wt _o $ polymer solid substance (pure polymer in comparison to the erfindungsgemäßeη polymer mixtures) # than 0.1 aqueous solution used "the 0.1% -lge aqueous polymer solution was prepared from the erfindungsgemäßeη water-in-oil dispersions prepared

The ash content of the leaves thus prepared was determined. The measured values are mean values from four samples »

Table 4 shows the superiority of the water-in-oil mixed dispersions prepared solution versus the mixture of the aqueous solution of the individual components »

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Table 4: retention effect

Product % ash in the sheet standard

Average value deviation S.

Aqueous solution directly 16.3 0.55

made from dispersion C.

Comparative examples:

without addition 7.2 0.55

Aqueous solution produced 14.7 0.50

represents by mixing
a 0.01 # aqueous solution A and
a 0.01 ^ aqueous solution of a copolymer from
0.846 moles of acrylamide
and 0.153 moles $ des
Sulphate of the diethylami noät hy lacry lat s

1.2 Lump size when flocculating municipal sewage sludge

The clogging of digested sludge from a municipal sewage treatment plant was assessed to be 2.3% by weight of solid. The sludge solids had an ash content of 40.4% by weight .

The sludge with defined amounts of polymers (pure polymers in comparison to the polymer mixtures according to the invention) as 0.1 # Aqueous Solutions Used «These solutions were based on the water-in-oil dispersions according to the invention (see Table 1) prepares «

The polymer solution was mixed well with the sludge by tilting the measuring cylinder back and forth six times, flocculation occurred. Subsequently, a Buchner funnel (11 cm diameter) was poured into the a round filter was inserted, filtered and, after a filtration time of 10 minutes, the flake size of the sludge flakes was assessed visually, where-

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with a rating scale from 1 (no plocking) to (very large, stable flake).

Table 5: Plocking of communal Paulschlamm "Flokkungsicherung from 1 (no plocking) to 5 (very large, stable flake)

Product blocking when added

amounts of polymer solids (g / m sludge)

100 150 200 250 300 350

Dispersion B 3 5

Dispersion D 4-5 5

Dispersion DA 3-4 5

Dispersion DB 2-3 4-5 5

Comparative examples;

Dispersion A 2 3 4-5 5

Solution A 1-2 1-2 1-2 1-2

Table 5 shows the superior synergistic effect. Only at an amount of 80 GewJ solution A will again reaches the level of the pure cationic polyacrylamides, although the pure solution A is essential in itself brings with it a weaker flocculation effect than the pure cationic polyacrylamide.

Example 2

As indicated in Example 1, a 25 # Water-in-oil dispersion of a copolymer of acrylamide with the Sulfate of diethylaminoethyl acrylate (molar ratio 0.846 / 0.153) (dispersion A) the 20 # aqueous solution B with an Ultraturrax emulsified.

The composition of the mixed dispersions obtained, side by side the cationic polyacrylamide and solution B contained in the discontinuous phase are shown in Table 1.

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Stable mixed dispersions are obtained in which, as can be seen in Examples 2.1 to 2.2 and Tables 6 to 8 is, a clear synergistic effect in the effect of the combination of both polymers teim use as retention and Drainage aid occurs in papermaking and in the plocking of municipal sewage sludge,

2.1 Effect of the dispersion in papermaking

2.1.1 Retention Effect

The test was carried out as described under Example 1.1.1.

Table 6 shows the superior synergistic effect »Only with an amount of 70 % of solution B is the level of pure cationic polyacrylamide reached again, although pure solution B has a significantly weaker effect than pure cationic polyacrylamide.

Table 6; Retention effect

[Polymer solid used: 0.015 wt.

Product % ash in the leaf

1.5 % alum; 0.5 % alum; pH -4.8 pH 6.0

Dispersion E 14.0 13.3

Dispersion P 14.1 13.1

Dispersion G 14.1 12.9

Dispersion GA 9.3 9.5

Comparative examples;

without addition 4.7 4.9

Dispersion A 12.9 12.8

Solution b. 7.6 8.4

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2.1.2 Acceleration of drainage

The test was carried out as described under Example 1.1.2.

Table 7 shows the superior synergistic effect.

Table 7: Reduction of the degree of grinding

[Polymer solid used: 0.04 %]

product Grind ⁰ SR Alum; 1.5 % alum; without , 0 pH 4.8 pH 7 36 Dispersion E 30th 34 Dispersion P 26th 37 Dispersion G 28 39 Dispersion GA 30th Comparative examples; 59 without addition 54 46 Dispersion A 42 43 Solution b 35

In the entire range studied the combination of the polymers is in the form of their water-in-oil dispersions, a compared with the pure blend components stronger Mahlgradsenkung which amounts to 9 ⁰ SR.

2.2 Flake size in the case of plocking municipal sewage sludge
The test was carried out as described under Example I ₀ 2.

Table 8 shows the superior synergistic effect. The level of the pure cationic polyacrylamide is only reached again when the amount of solution B is 80% , although the pure solution B itself has a significantly weaker blocking effect than the pure cationic polyacrylamide.

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Table 8: Flocculation of municipal digested sludge. Flocculation Rating from 1 (no flocculation) to 5 (very large, stable flake)

Product flocculation when added

amounts of polymer solids (g / no sludge)

250 300 350

100 I50 200 250 Dispersion E
Dispersion F
Dispersion G
Dispersion GA 2-3
3 5
5
3-4
2 5
5
4-5 5 Comparative tests: Dispersion A
Solution b 2 3
1 4-5
1-2 5
1-2 Example 3

Analogously to that given in Example 1, the 20% aqueous solution C was poured into a 25% water-in-oil dispersion of a copolymer of acrylamide with the sulfate of diethylaminoethyl acrylate (molar ratio 0.846 / 0.153) (dispersion A) using an Ultraturrax emulsified - The composition of the mixed dispersions obtained, which contain the cationic polyacrylamide and the polymer of solution C side by side in the discontinuous phase, is given in Table 1.

Stable mixed dispersions are obtained in which, as in Examples 3 »1 to 3.2 and Tables 1 to 11 can be seen, a clear synergistic effect in the effect of the combination of the two polymers when used as Retention and drainage aids in paper production and in the flocculation of municipal waste water occurs.

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3.1 Effect of the dispersion in papermaking

3.1.1 Retention Effect

The test was carried out as described under Example I ₀ I ₀ I »

Table 9 shows the superior synergistic effect _o Only with an amount of 60 to 80 % of the polymer of solution C is the level of the pure cationic polyacrylamide reached again, although the pure solution C has a significantly weaker effect than the pure cationic polyacrylamide »

Table 9; Retention effect

[Polymer solid employed: 0.015% by weight |

Product % ash in the leaf

1.5 % alum; 0.5 % alum; pH 4.8 pH 6.0

Dispersion H 13.5 13.9 Dispersion I '13.9 13.2 Dispersion J 11.0 11.6 Dispersion K 11.1 10.8 Comparative examples ι without addition 4.2 4.9 Dispersion A 12.6 9.8 Solution C 6.5 5.9

ο 1ο 2 dewatering acceleration

The test was carried out as described in Example 1 "1» 2 »

Table 10 shows the superior synergistic effect,

Table 10: Reduction of the grinding degree

[Polymer solids used: 0.04 % \

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H 5 A. 1.5 0. 2552014 I. pH 4 Line 31 βδβ J 23 Grind ⁰ SR product K 25th % Alum; without Comparative tests: 26th , 8 pH 7 Alum; without addition 28 44 , 0 Dispersion Dispersion 45 Dispersion Solution C 56 46 Dispersion 32 46 Dispersion 45 57 50 47

In the entire range studied, the combination shows the shape of the polymers in the form of water-in-oil dispersions, a compared with the pure blend components stronger Mahlgradsenkung which amounts to 9 ⁰ SR.

Flocculation size in the flocculation of municipal wastewater mud

The test was carried out as described under Example 1 »2

Table 11 shows the superior synergistic effect. Only with an amount of 80 % of the polymer of solution C is the level of the pure cationic polyacrylamide again reached, although the pure solution C itself has a much weaker flocculation effect than the pure cationic polyacrylamide.

Table 11: Flocculation of municipal digested sludge. Flocculation Assessment from 1 (no flocculation) to 5 (very large, stable flake)

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Blocking with the specified quantities of polymer solids added (g / m- ⁵ sludge)

100 150 200 250 300 350 400

Dispersion H
Dispersion I
Dispersion J
Dispersion K 4th
4th
3 .sr
in in in ι
ro 5 Comparative examples: Dispersion A
Solution C 3-4
1-2 5
1-2 1-2

Example 4

Analogously to that given in Example 1, a 25/5 was Water-in-oil dispersion of a copolymer of acrylamide with the sulfate of diethylaminoethyl acrylate (molar ratio 0.846 / 0.153) (dispersion A) the 20-year aqueous solution D emulsified with an Ultraturrax. The composition of the mixed dispersions obtained, the cationic Polyacrylamide and the polymer of the solution D contained in the discontxnuxerlxchen phase is shown in Table 1.

Stable mixed dispersions are obtained in which, as can be seen in Examples 4.1 and 4.2 and Tables 12 and 13 is, a synergistic effect in the effect of the combination of both polymers when used as retention and drainage aids occurs in papermaking.

4.1 Retention Effect

The test was carried out as in example 1.1.1.

Table 12: retention effect

Polymer solids used: 0.015% by weight \

70982 1/0852

_ ₂₃ _

product % Ashes 2552014 - * 5 - 1.5 % alum; O.Z. Jl 686 pH 4.8 Dispersion L 11.9 in the sheet Dispersion M 12.3 0.5 % alum; Dispersion N 11.5 pH 6.0 Dispersion 0 10.9 9.8 Comparative examples; 10.5 without addition 4.2 11.3 Dispersion A 12.6 10.0 Solution D 6.1 4.9 9.8 7.0

Table 12 shows that in spite ,, replacement of up to 80 percent of the condition.% Better effective cationic Polyacryland ds in the mixture by the weaker effective polymer solution D, the high activity level of cationic polyacrylamide bleibte

4 "2 Dewatering acceleration The test was carried out as described under Example I ₀ I ₀ 2"

Table 13s Reduction of the degree of grinding

[Polymer solids used 0.04 % ~ \

Product grind ⁰ SR

nanigraae οη

1.5 % alum; without alum; pH 4.8 pH 7.0

Dispersion L 28 48 Dispersion M 30th 50 Dispersion N 31 50 Dispersion 0 37 53 Comparative tests: without addition 56 57 Dispersion A 32 50 Solution D 48 56

7 0 9821/0852

25520H

ο.ζ. 51 686

fs *

Table 13 shows that despite the replacement of up to 60 wt. of the more effective cationic polyacrylamide in of the mixture due to the less effective polymer of solution D, the higher level of effectiveness of the cationic Surprisingly obtained polyacrylamide bIe ib t ο

Example 5

Analogously to that given in Example 1, the 20% aqueous solution E was emulsified with an Ultraturrax into a 25% water-in-oil dispersion of a copolymer of acrylamide with the sulfate of diethylaminoethyl acrylate (molar ratio 0.846 / 0.153) (dispersion A) . The composition of the mixed dispersions obtained, which contain the cationic polyacrylamide and the polymer of solution E side by side in the discontinuous phase, is given in Table 1 =

Stable mixed dispersions are obtained in which, as can be seen in Examples 5 »1 and 502 and Tables 14 and 15 is, a synergistic effect in the effect of the combination of both polymers when used as retention and drainage aids occurs in papermaking »

5ol retention effect

The test was carried out as described under Example 1.1.1 »

Table 14: retention effect

[Polymer solid used 0.015 wt.

Product % ash in the leaf

Dispersion P Dispersion Q Dispersion R Dispersion S Comparative Examples; without addition
Dispersion A Solution E

70982 1/0852

1.5 % alum; 0.5 % alum; pH 4.8 pH 6.0 14.0 14.6 14.8 13.8 12.9 13.3 13.2 11.9 5.0 * .5 14.5 14.1 9.1 9.2

255 "2OH

Oz J> l 686

Table 14 shows that despite replacement of up to about 50 wt.; the more effective polyacrylamide in the mixture the less effective polymer of solution E obtained the high level of effectiveness of the cationic polyacrylamide remain.

5.2 Acceleration of drainage

The test was carried out as described in Example 1 "1.2"

Table 15: Reduction of the grinding degree

[Polymer solid used: 0.04 %

product Grind ⁰ SR 1.5 % alum; without alum; pH 4.8 pH 7.0 Dispersion P 29 46 Dispersion Q 27 42 Dispersion R 28 43 Dispersion S 33 45 Comparative example without addition 53 58 Dispersion A 31 47 Solution E 38 48

Table 15 shows that despite the use of up to 60 of the more effective cationic polyacrylamide in the Mixing through the less effective polymer of solution E a slight improvement in the level of effectiveness of the cationic polyacrylamide occurs »

Example 6

Analogously to that given in Example 1, the 20 SS aqueous solution A was emulsified into a 25% water-in-oil dispersion of a homopolymer of acrylamide (dispersion T) using an Ultraturrax the acrylamide homopolymer and the polymer of solution A contained in the discontinuous phase is given in Table 1 «709821/0852

- O.Z. 31 686

Stable mixed dispersions are obtained in which, as can be seen from Example 6.1 and Table 16, a synergistic one Effect in the action of the combination of the two polymers when used as retention aids in papermaking on τ occurs.

6.1 Retention effect

The test was carried out as described under Example 1.1.1 »

Table 16: retention effect

[Polymer solids used: 0.015% by weight \

Product % ash in the leaf

1.5 % alum; 0.5 % alum; pH 4.8 pH 6.0 Dispersion U 13.0 12.7 Dispersion V 12.0 12.5 Dispersion W 11.8 12.1 Dispersion X 11.7 11.3 Dispersion Y 10.8 11.0 Dispersion Z 10.0 8.1 Comparative examples: without addition 5.1 4.8 Dispersion T 12.7 13.0 Solution a 8.8 7.4

Table 16 shows that despite the replacement of up to about 50% by weight of the more effective polyacrylamide in the mixture the less effective polymer of solution A obtained the relatively high level of effectiveness of the polyacrylamide remain"

09821/0852

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Claims (5)

O.ζ. 31 686 patent claims 2 5 5 2 Ü 1 4 1. Mixtures based on water-soluble, nonionic or cationic polymers of acrylamide and water-soluble resinous amino condensation products, characterized in that they are present in the discontinuous phase of a water-in-oil dispersion. 2. Mixtures according to claim 1, characterized in that they contain 95 to 40 wt.? of a neutral or cationic acrylamide polymer and 5 to 60% by weight of a water-soluble resinous amino condensation product. 3. Mixtures according to claims 1 and ο 2, characterized in that the aqueous phase of the dispersion 40 to 85 GeWoiSj based on the total dispersion, is and having a solids content of 15 to 50 wt _o # 4. Mixtures according to Claims 1 to 3 _S, characterized in that the cationic acrylamide copolymers contain units of esters of amino alcohols of acrylic acid or methacrylic acid and amides of dialkylaminoalkylamines of acrylic acid or methacrylic acid in copolymerized form » 5. Mixture according to claims 1 to 4, characterized in that the water-soluble resinous amino condensation product used is polyalkyleneimines, alkyleneimine-epichlorohydrin resins, polyamidoamines or reaction products of alkyleneimines with aminopolyamides » BASF Aktiengesellschaft ^ 709 8 21/085 2 ORIGINAL INSPECTED