FI63385B - STABIL DISPERSION AV VATTEN-I-OLJATYP FOER ANVAENDNING SOM KOAGULERINGS- SEDIMENTATIONS- AVVATTNINGS- OCH RETENTIONSMEDEL OCH FOERFARANDE FOER FRAMSTAELLNING AV DENNA - Google Patents

Description

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_ '(44) Date of entry into force of the

Patent- och reflsterstyrelsen '· Subject matter of the application and of the Treaty 28.02.83 (32) (33) (31) Privilege requested — Begird prlorltut QU .07.73

Saxony Federal Republic-Förbundsrepubliken Tyskland (DE) P 2333927-7 (71) Chemische Fabrik Stockhausen GmbH., Bäkerpfad 25, Ul50 Krefeld,

Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (72) Kurt Dahmen, Rheydt, Wolfgang Hiibner, Kempen, Eduard Barthell,

Krefeld, Federal Republic of Germany Förbundsrepubliken Tyskland (DE) (Tb) Oy Kolster Ab (5I +) Stable water-in-oil dispersion for use as flocculation, sedimentation, dewatering and retention agents and method for its preparation - Stabil dispersion av vatten-i-olja -types for coagulation, sedimentation, awakening and retention and ocean retrieval

Water-soluble, powdered polymeric materials are known as coagulation, sedimentation, dewatering and retention aids. It is further known that the higher the molecular weight of powdered, water-soluble polymeric materials, the more effective the use of such products. High molecular weights mean that the preparation of working solutions from water-soluble, powdered high molecular weight substances is time consuming and difficult, i.e. the existence of a working solution free of particles is not always certain. In addition to this, the use of powdered products is usually technically difficult and expensive equipment is required for its continuous, constant dosing.

All these difficulties are eliminated if flowable or at least pumpable products are used, in which case the economical requirement is that the concentration of active substance in such flowable or pumpable products is as high as 2 63385 possible. In view of the high viscosity of concentrated aqueous solutions of high molecular weight, water-soluble substances, the above requirement has not yet been met.

It has now been found that flocculation, sedimentation, dewatering and retention aids which meet the above requirements are obtained in the required sealable form and containing a high proportion of active substance when water-soluble, high molecular weight H-active substances are dispersed in a concentration of 10-50 % by weight, preferably at a concentration of 25-35% by weight, in a water / oil emulsion and reacting the dispersion thus obtained under Mannich reaction conditions with monomeric and / or polymeric formaldehyde, preferably using an aqueous formaldehyde solution emulsified in the organic phase, and a primary and / or secondary amine . In this case, it is possible to control the content of the polymeric, water-soluble Mannich base in the final product by means of equivalent or equivalent amounts of formaldehyde and amine with dispersed polymeric H-active compounds. It was further discovered that the products of the invention are obtained in the same way as water-soluble monomeric Mannich bases in a water / oil emulsion are polymerized.

The water-in-oil type stable dispersion according to the invention is thus characterized in that the dispersed phase contains water and a water-soluble Mannich base of the acrylamide or methacrylamide polymer and the continuous phase consists of a water-insoluble hydrophobic liquid, preferably an aromatic and / or aliphatic the amount of water-in-oil type emulsifier and the amount of polymeric Mannich base in the dispersion is 10 to 50% by weight, preferably 25 to 35% by weight. The process according to the invention is characterized in that an acrylamide or methacrylamide polymer emulsion containing either a water-in-oil emulsifier is reacted with a monomeric or polymeric formaldehyde and an amine of the formula R-NH2 and / or an amine of the formula R-NH-R 'and R R 'are alkyl and / or alkanol groups having 1 to 18 carbon atoms or the Mannich base of the monomeric acrylamide or methacrylamide is first prepared in aqueous solution and then polymerized in a water-in-oil emulsion containing a water-in-oil emulsifier in a manner known per se.

Suitable water-oil emulsion-dispersible substances suitable for the Mannich reaction with active hydrogen are, in particular, acrylamide, methacrylamide or their polymeric poly-acrylamide and polymethacrylamide or copolymers thereof with other polymerizable compounds. Particularly suitable are polymers and copolymers of acrylamide, such as polyacrylamide, and copolymers of acrylamide with acrylonitrile, salts of acrylic acid, acrylic acid esters, styrene, vinyl acetate, vinyl chloride, vinyl chloride, vinylpyrrolidone, vinyl

Suitable amines for the reaction with a compound containing active hydrogen are amines of the formula R-NH2 and / or R-NH-R ', in which R and R' are alkyl radicals and / or alkanol groups having 1 to 18 carbon atoms. Particularly suitable for the purposes of the invention are straight-chain amines which have no more than 8, preferably no more than 6, carbon atoms in the alkyl or alkanol groups. Thus, suitable amines include, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine and octylamine. Of the straight chain amines, secondary amines are most preferred for purposes of the invention. Particularly suitable secondary amines are, for example, dimethylamine and diethylamine. An example of an alkanolamine is diethanolamine.

To prepare a stabilized system for dispersing a water-soluble, H-active monomer, polymer and / or copolymer, a water / oil emulsion is used. as the oily phase, aliphatic and / or aromatic hydrocarbons are useful. The water / oil emulsion is obtained using emulsifiers with a corresponding HLB number (hydrophilic-lipophilic balance), in particular sorbitan esters and other oil-soluble fatty acid esters, such as fatty acid polyglycol esters.

A particular advantage of the products obtained according to said process is that they have an active ingredient content of 10, generally 30% but also 50% by weight, that the dispersions are stable and that the preparation of working solutions from these dispersions can take place without high technical costs, for example by means of a dosing pump. In this case, when diluting the polymer product with water without the aid of additional wetting agents, it quickly enters the solution completely.

The method according to the invention offers considerable advantages over the following already known methods.

U.S. Patent 3,539,535 describes a process for obtaining solid, cationically active polymers in which a polyacrylamide suspension is prepared in an organic solvent without the use of an emulsifier. This volatile suspension is then converted into Mannich base with formaldehyde and secondary amines and isolated as a solid by precipitation with suitable solvents. The suspensions described in the publication are volatile intermediates and therefore cannot be used directly as a coagulant, sedimentation, dewatering or sedimentation agent. In addition, the products according to the publication having a polymer concentration of more than 10% by weight contain 0.2-15% by volume of insoluble matter (US 3,539,535), Table I), due to the tendency of such a concentrated solution to form crosslinked gels. Even small amounts of insoluble ingredients adversely affect the usefulness of the product as a flocculant and dewatering agent in papermaking, as they are invariably visible in the finished paper.

German application EE 2 048 664, 2 054 523, 2 156 858, 2 206 564 and 1 546 344 discloses the preparation and use of aqueous solutions of polyacrylamide-Mannich bases obtained by aminomethylation of acid amide groups in dissolved polymer products with formaldehyde and amine. However, due to the high degree of polymerization of the polyacrylamide required for the potency or the state of this polymer in the aqueous solution, only relatively dilute, i.e. 5-10% by weight polymer solutions can be prepared by this method. Solutions already have a high viscosity at this concentration of active substance. The rigid products produced by this method are therefore difficult to transport or handle, so that their use in various fields, despite their good effect, is limited.

When stored for a longer period, as well as in attempts to remove water from these products or to manufacture them at higher concentrations of the active substance, cross-linking to substantially insoluble and thus ineffective substances can be observed.

According to the process described in German application DE 2 163 246, powdered polyacrylamide Mannich steel grains are obtained by treating 5-10% aqueous polymer solutions obtained according to the process described above, said process according to which polymers are precipitated from a dilute aqueous solution by adding polyvalent separated and the product dried, again incurring costs. The disadvantages of the process are the same as those described in U.S. Patent 3,539,535, and it is clear from the publication that it has not been possible to prepare acrylamide or methoxylamide. Completely water-soluble solutions or emulsions of Mannich bases at concentrations of 10-50%, since insoluble products have already been formed at a concentration of about 10%.

63385

"Acryl- und Metacrylverbindungen", 1967, p. 358, describes the reaction between polyacrylamide, formaldehyde and secondary amines. However, based on said publication, it is not possible to prepare highly concentrated, flowable Mannich base products according to the present invention.

Also known in the prior art is German Offenlegungsschrift DE 1 442 398, which describes solid, free-flowing flocculation compositions formed from a reaction product of polyacrylamide and dialkylammonium salts and paraformaldehyde which, when dissolved in a medium having a suitable pH, act cationically.

The products prepared by the process of the invention can be used in various fields. They can be used as sedimentation or flocculation aids in a heterogeneous liquid-solid system, for example in the sedimentation of aqueous aqueous suspensions, and also as dewatering and retention aids. In this way, it is also possible to use such water-in-oil suspensions in aqueous but predominantly non-polar liquid systems.

The manufacturing methods and use of the products are illustrated by the following examples.

The organic, water-repellent phase (I) used in Examples 1-10, which is an essential component of the product, can be obtained, for example, by mixing 138 parts of n-paraffin having the following characteristics:

Boiling range: 195-225 ° C, Density 0.740

Proportion of hydrocarbons in the mixture: up to% by weight C10 8 C11 38 C12 37 C13 16 18 parts of sorbitan monooleate, and 12 parts of stearic acid polyglycol ester containing 10 moles of ethylene oxide per mole of stearic acid.

Example 1

Stock mixture: 140 parts of polyacrylamide latex prepared in a known manner by radical polymerization of 3,135 parts of acrylamide dissolved in 2,660 parts of water, together emulsified in 4,104 parts of organic phase (I) mixed with 23.1 parts of a 60% aqueous dimethylamine solution, emulsified in 16.9 parts of organic phase (I) with mechanical stirring. After about 60 minutes, a second emulsion of 23.1 parts of an aqueous 40% formaldehyde solution and 16.9 parts of the organic phase (I) is added portionwise with stirring so that the temperature of the mixture, due to the heat of reaction generated, does not exceed 40 ° C. After 4 hours, the reaction is complete and the product is obtained as an easy-to-flow, colorless turbid polymer suspension containing 27.9% by weight of polymeric Mannich base.

Example 2

Stock mixture: 200 parts of polymer latex (as in Example 1) are mixed with 9.0 parts of a 60% aqueous solution of dimethylamine, 8.7 parts of diethylamine and 0.3 parts of water in 12 parts of organic phase (I) and subjected to then react with 17.9 parts of an aqueous 40% formaldehyde solution in 12 parts of organic phase (I) in the same manner as described in Example 1. A polyacrylamide-Mannich base suspension with 32.7% water-soluble polymer is obtained.

Example 3

Starting mixture: 136.3 parts of polyacrylamide latex (as in Example 1) are reacted with a total of 45.2 parts of 60% dimethylamine in 28.2 parts of the organic phase (I) and with a total of 45.2 parts of aqueous 40% formaldehyde solution in 28.2 parts of organic phase (I). In this case, the procedure is to first add one third of the amine emulsion to the polymer latex with stirring and, after continuous stirring for 20 minutes, one third of the aldehyde emulsion is added. The temperature of the mixture must not exceed 40 ° C. After a reaction time of 30 minutes, the remaining amine or aldehyde emulsions are individually reacted in the same manner, i.e. in 1/3 of the starting amounts, to react completely according to the times mentioned. A flowable, clear product is obtained which is water soluble. Its active ingredient content is 26.3% by weight.

Example 4

Initial mixture: 128 parts of acrylamide dissolved in 108 parts of water are mixed with 66 parts of diethylamine. 67.5 parts of an aqueous 40% formaldehyde solution are introduced portionwise into the mixture so that the temperature does not exceed 40 ° C due to the heat of reaction generated in the mixture.

63 parts of the resulting solution of carbonylmethylamine and acrylamide in a ratio of about 0.6: 0.4 in water are mixed with 50 7 63385 parts of the organic phase (I) and 11 parts of water. With stirring, the mixture is converted into an emulsion and saturated with oxygen. An oxidation-reduction system containing 0.023% by weight of ammonium peroxide disulphate, 0.023% by weight of potassium bisulphate and 0.004% by weight (based on monomers) of ferrous sulphate is added to the emulsion and polymerisation at 35 ° C for 10 hours gives polyacrylamide. Mannich-base suspension; active substance content: 28.2% by weight.

Example 5 300 parts of 31.35% polyacrylamide latex (corresponding to Example 1) are mixed under mechanical stirring at room temperature in portions with a W / 0 emulsion prepared by pre-cooling with 138.5 parts of diethanolamine, 50 parts of water and 99.5 parts of part of 40% formalin and 148 parts of organic phase (I). After a reaction time of about 5 hours, a 33.7% cationically active polymer suspension has formed.

Example 6

In the same manner as described in Example 5, 200 parts of polyacrylamide latex are reacted with a W / o emulsion of 77.5 parts of 40% methylamine, 66.0 parts of 40% formalin and 120.0 parts of organic phase ( I). The product contains 22.8% of active ingredient.

Example 7 300.0 parts of a 28% copolymer latex prepared in a known manner by radical copolymerization of 75.0 parts of acrylamide and 25.0 parts of dimethylaminoethyl methacrylate hydrochloride emulsified in 140.85 parts of water and 117.5 parts of the organic phase (I) are first mixed with 5 parts of a W / O emulsion containing 50 parts of 60% dimethylamine and 40 parts of the organic phase (I). This raises the pH of the latex to 8.0. With cooling, 20 parts of 60% dimethylamine and 20 parts of 40% formalin are mixed with 20 parts of organic phase (I) and this mixture is again added as a W / O emulsion dropwise to the copolymer latex. After 5 hours, a polymeric Mannich base suspension with 26.8% of active ingredient is formed.

Example 8 99.5 parts of a 60% dimethylamine solution and 99.5 parts of a 40% formalin are combined under cooling and emulsified with mechanical stirring after the addition of 96 parts of the organic phase (I). The resulting W / 0 emulsion is added with stirring to 316 parts of a 31% polymer latex obtained by copolymerizing 95 parts of acrylamide and 5 parts of acrylonitrile in a W / 0-8 63385 emulsion according to the preparation method of Example 1. The reaction mixture is kept at room temperature for 5 hours and stirred to give a cationically active product containing 28.3% of active ingredient.

63 parts of the resulting solution of carbamoylamine and acrylamide in a ratio of about 0.6: 0.4 in water are mixed with 50 parts of the organic phase (I) and 11 parts of water. Under stirring, the mixture is converted into an emulsion and saturated with oxygen. An oxidation / reduction system containing 0.023% by weight of ammonium peroxide sulphate, 0.023% by weight of potassium bisulphite and 0.004% by weight (based on monomers) of ferrous sulphate is added to the emulsion and polymerisation at 35 ° C for 10 hours gives polyacrylamide. Mannich base suspension: active ingredient content: 28.2% by weight.

Example 9

In the same manner as described in Example 1, a water / oil emulsion is prepared from 67.5 parts of 60% diraethylamine, 67.5 parts of 40% formalin and 100.0 parts of organic phase (I) and added to the polymer latex with stirring. has been prepared in a known manner by radical polymerization of a monomer emulsion containing 80.0 parts of acrylamide, 10.3 parts of 2-vinyl-5-ethylpyridine quaternized with dimethyl sulphate (9.7 parts) and 240 parts of water and 350 parts organic base (I). A cationically active polymer suspension with a concentration of 16.8% is formed.

Example 10 152.0 parts of a copolymer latex comprising a part of 20.0 parts of acrylamide and a part of 7.8 parts of vinylpyrrolidone, 50.0 parts of water and 74.4 parts of organic phase are mixed with mechanical stirring at room temperature with a W / O emulsion containing 10.6 parts of 60% diraethylamine which, under cooling, was mixed with 10.6 parts of 40% formalin and 15.7 parts of the organic phase (I). After a reaction time of 5 hours, a 19.0% polymer-Mannich base suspension is formed.

Example 11

The products prepared according to the invention were tested as sedimenting agents in flocculation experiments. By determining the sedimentation rate, the coagulation behavior of polyacrylamide-Mannich bases in aqueous solution after addition to aqueous clay suspensions prepared in the usual manner by slurrying kaolin in water and adjusting the pH to about 4 ° C was studied. The results are shown in Table I: 63385 9

Table I ......

Product Time (s) Product from example Time (s) without 180 6 9.3

From Example 1 8.9 7 10.4 2 8.3 8 9.1 3 11.6 9 11.6 4 15.3 10 12.7

Table I: Flocculation efficiency for a turbid clay slurry with a solids content of 20 g / l using Al 2 (SO 2) - j addition, product in 0.1% solution: concentration 4 ppm (parts per million). For performing the test, cf. H. Akyel / M. Neven: Chemie-Ing.-Technik 39 (1967) 172.

Example 12

Similarly, polyacrylamide-Mannich base suspensions are useful in the preparation of titanium solutions, so-called in the clarification process of "black solutions" which form an intermediate step in the preparation of TiCl 2 pigments from ilmenite or ore slag.

To 1 liter of titanium solution is added 7.5 ml of a 0.1% solution of the product obtained in Example 3. After the addition of the flocculant, the sample is shaken for 15 seconds and filled into a 1 liter beaker.

The effect manifests itself as rapid flocculation; landing speed: 6 m / hour. Flocculation efficiency can be further evaluated by the gray filter scale values or flocculation quality shown in Table II, comparing the product of Example 3 of the invention with a commercially available flocculant based on trimethylammonium methyl methacrylate, hitherto used to clarify "black solutions".

Table H

Flocculant Gray filter scale (residue in mg in 50 ml of remaining solution) after 30-60-120 minutes

Product of Example 397 5

Product based on trimethylammonium methyl methacrylate 11 10 8

Example 13

The utility of the products as dewatering or retention agents in papermaking is illustrated by the studies described below.

10 63385 From standardized cellulose slurries having a blend of bleached cellulose, spruce and beech 70:30, a consistency of 3 g / l degree of grinding 69 S.R.

pigmentation 25% kaolin based on cellulose gluing 1% resin glue acidified with 3%:

with an aqueous solution of Al2 (PO4) 3

6.5-6.8, the rate of water removal as a change in the degree of Schopper-Riegler (° S.R.) grinding as a function of product addition and the retention capacity of these products were measured by gravimetrically determining the solids content in the effluent of a sheet former (Rapid-Köphen). The results are summarized in Table III.

Table III

Dewatering tests grind- Retention test solids degree (° S.R.) With added concentration-wire water

Excipient 100-200-300-300-200-300 ppm Product of Example 1 57 53 47 156 132 129 Product of Example 7 59 55 50 161 140 135 Copolymer of acrylamide and trimethylammonium methyl methacrylate 60 58 54 176 152 146 without increase 69 ° SR

i__ -__! _ It appears that the products of the invention are effective under these experimental conditions, which are approximately equivalent to the research methods used in paper technology. In addition, since the products are easy to flow and therefore simple to handle, i.e. easy to dispense and easy to dissolve, they can be advantageously used in papermaking.

Example 14

The products described can also be used to remove water from sewage sludge. Drainage test for sewage sludge:

Claims (2)

63385 11 Dewatering agent Addition amount Solid Appearance (g / m 2) substance extinction (%) (x100) Product of Example 1 93 31.1 clear 20 Highly copolymer of acrylamide and trimethyl-well ammonium ethyl methacrylate 220 30.2 cloudy 100 Example 6 105 32, 4 clear 22 "7 98 31.4" 20 A stable water-in-oil type dispersion for use as a flocculant, sedimentation, dewatering and retention agent, characterized in that the dispersion phase contains water and a water-soluble Mannich base of a water-soluble acrylamide or methacrylamide polymer and the continuous phase consists of a water-free hydrophobic base liquid, preferably aromatic and / or aliphatic hydrocarbons, the dispersion containing a stabilizing amount of a water-in-oil type emulsifier, and the amount of polymeric Mannich base in the dispersion is 10 to 50% by weight, preferably 25 to 35% by weight. Process for preparing a stable water-in-oil dispersion according to Claim 1, characterized in that an acrylamide or methacrylamide polymer emulsion containing either a water-in-oil emulsifier is reacted with a monomeric or polymeric formaldehyde and an amine of the formula R-NH 2 and R-NH With an amine according to -R ', wherein R and R' are alkyl and / or alkanol groups having 1 to 18 carbon atoms, or a Mannich base of a monomeric acrylamide or methacrylamide is first prepared in aqueous solution and then polymerized in a manner known per se in an oil-in-emulsion containing a water-in-oil emulsifier.