EP0000714A2 - Auxiliary agent for the improvement of retention, dehydration and preparation, especially for the manufacture of paper - Google Patents

Abstract

The invention relates to an aid for improving the retention of washable solids, for accelerating the dewatering of suspensions and for the faster processing of industrial water, waste water and sludge, this aid being present as an aqueous polymer solution of a basic water-soluble polymer and thus formed from a partial product A and a further partial product B. is that the intermediate AB obtained is reacted with polyfunctional compounds. The partial product A is first formed by the action of polyvalent aliphatic amines on the reaction product from a polyethylene glycol with epichlorohydrin. Separately from this, the second partial product B is formed from at least one polyalkylene polyamine and / or at least one aminocarboxylic acid or its lactam and / or hexamethylene diammonium adipate. The intermediate product AB is formed by reaction of the halogen groups of sub-product A with the -HN groups of sub-product B with elimination of hydrohalic acids. The intermediate AB described above with polyfunctional compounds to the reaction product C is mainly used in the paper manufacturing industry.

Description

The invention relates to an aid for improving the retention of washable solids, for accelerating the dewatering of suspensions and for the faster treatment of industrial water, waste water and sludge by adding basic water-soluble polymers as an aqueous polymer solution, in particular in the paper industry.

Such polymers and their use in the above-mentioned sense in papermaking are already known in the art from numerous publications. For example, DT-AS 15 46 290 describes reaction products made from polyalkylene polyamines and bifunctional polyalkylene oxide derivatives which are suitable for the flotation of fibers and fillers from paper machine waste water, but not at the same time, as would be desirable, for use as retention and Drainage aids are equally suitable in the paper industry. In US-PS 35 75 797 viscous flotation agents for paper machine waste water are described. These flotation agents are reaction products of polyalkylene polyanines with polyethylene glycol derivatives which contain at least 2 chloroformate groups. Unfortunately, these products can only be prepared as a 10% solution and, moreover, have only relatively low retention and drainage capacities on.

Other aids recommended for the above-mentioned purpose can be seen in DT-OS 21 62 567. Here, a polyamino amide (production of the polyamino amide, for example, by condensation of adipic acid and diethylenetriamine) via the CH2 Cl groups is attached to a polyether with a filiform molecular structure and terminal tertiary amino groups (production of the polyether, for example from glycol, epichlorohydrin and dimethylamine) and this addition product then reacted with epichlorohydrin. The aforementioned adduct is already highly branched, so that when it is subsequently crosslinked with epichlorohydrin, it leads to a considerably entangled molecular structure, which has a disadvantageous effect when this auxiliary is used when it is used as a retention and drainage agent, because only a fraction of this is due to this entangled molecular structure Aid molecule in the above Meaning can take full effect.

In the DT-AS 21 27 082, which is also to be mentioned in this context, a complicated process for the production of drainage and retention aids is described, the cross-linking of the reaction products of polyepichlorohydrin and polyamides with bis-chlorohydrin resulting in relatively unfavorable molecular structures, which in themselves existing high cationic charge of the molecule does not fully develop when used as mentioned at the beginning and therefore does not show optimal performance in paper production.

The same applies to that from DT-OS 22 55 586 Liche product that only shows polyethylene glycol as an additional building block with an otherwise basically equivalent structure.

In the DT-DS 22 44 513 to be cited in this connection, similar products are known which are composed of polyepichlorohydrin, diamine and polyalkylene polyamines with subsequent crosslinking, for example with epichlorohydrin. However, due to the given structure, these products are also insufficient to be used as flocculation, retention and, at the same time, as drainage aids in papermaking.

Still other products have become known from DT-OS'n 24 34 816 and the associated additional DT-OS 25 15 760. Here, polyaminoamides made from polyglycol ethers and epichlorohydrin are reacted with crosslinking agents until a desired viscosity is achieved. However, here too molecular structures are unfavorable for the intended use in the paper industry, the lack of amino groups in the large ethylene oxide molecules in particular resulting in a stronger pH dependency and thus a reduced effectiveness.

In the DT-OS 24 36 386 which is finally to be mentioned in this connection, polyethylene polyamines having 15 to 500 alkyleneimine units with a crosslinking agent, obtained from the reaction of polyalkylene glycol ether with epichlorohydrin, are present in amounts of 0.08 to 0.001 mol of crosslinking agent per 1 equivalent of nitrogen in the polyalkylene polyamine to react and thus to crosslink.

Apart from the concerns that one has when using alkyleneimines as pure starting materials because of their carcinogenic properties, one has to think of the high technical outlay for safely carrying out the aforementioned reaction. This has a negative impact on manufacturing costs. Furthermore, the polyalkylene glycols mentioned here cannot provide a particularly favorable retention and drainage performance owing to their connection to the specific type of other building blocks of the macromolecule due to the above structure.

The prior art recognized above describes products which contain polyalkylene glycol compounds as the product component. If these products are used as retention agents, it should be remembered that polyalkylene glycols do not have any cationic charges recognized as necessary by experts in order to achieve a favorable retention performance.

Therefore, the continuously ongoing task of continuously improving the retention performance of such products has long led to the fact that they had previously been considered necessary for other reasons because of the installation of a polyalkylene glycol building block. The retention agents which have become known so far in this connection in this connection are now listed in the following prior art assessment. First of all, reference should be made to DT-PS 17 71 814, in which the use of basic polyaminoamides to increase the retention of fillers and pigments in papermaking, to accelerate the process Watering of paper stock suspensions and for processing paper machine wastewater by filtration, sedimentation and flotation by adding basic polyamides to the paper stock suspensions and / or the paper machine wastewater is described. The basic polyamides used are high molecular weight water-soluble products which are obtained by the action of compounds which are polyfunctional with respect to amino groups on basic polyamides dissolved or dispersed in water from polyvalent amines, dicarboxylic acids and aminocarboxylic acids or lactams containing at least three carbon atoms, and for their preparation from 1 val of the basic amino groups contained in the basic polyamides, less than 1 val of reactive groups were used in the polyfunctional compounds. Here, the polyalkylene polyamines are crosslinked with, for example, epichlorohydrin. The resulting acidic product has a structure that lacks cationic side chains, for example, due to the fact that the starting blocks are interconnected, which is why optimal reaction and drainage performance cannot yet be achieved.

A further development in this direction is the applicant's older proposal, based on French patent specification 20 94 645, in the form of DT-OS 23 53 430. This proposal is directed to the production and use of water-soluble papermaking aids based on polyamino amides, the dimeric fatty acids specified in the aforementioned French patent as the prior art being part of the starting monomer mixture for the production of a retention-effective macromolecule in the paper manufacture tion in the aforementioned DT-OS 23 53 430 have been replaced by short but cation-active and therefore more effective retention chains. In principle, in this DT-OS, basic polyaminoamides are reacted with ammonium compounds prepared by the action of a polyfunctional compound on a tertiary amine before they are mixed with polyfunctional crosslinking agents, such as, for example, epichlorohydrin. Although this known macromolecular compound shows a significantly better retention performance than practically all of the products known from the prior art cited above, the retention, drainage and water treatment achievements which can be achieved therewith have also not been completely satisfactory in papermaking.

The continuously ongoing task of creating appropriate aids with an ever increasing retention rate led to the development of a different macromolecule than the one described in the previously described DT-OS 23 53 430, namely as described in DT-PS'n 25 02 874 and 25 38 745 (addition to 25 02 874) can be seen. Products with special sedimentation performance are created here, whereby these are linked by linking polyaminoamides and polyamines, which are caused by the action of mono- or polyvalent amines on the environment. Settlement product from dimethylamines and epichlorohydrin. be obtained by means of epichlorohydrin. In this way, molecular spatial structures are created, which guarantee a very good effect in paper production in the acidic and neutral pH range, but are optimally conceivable and still by the specialist not yet achieve the desired services in the world.

In summary, with regard to the prior art listed above, it should be noted that neither the products described there, the polyethylene glycols as a building block nor the products, the polyaminoamides as building blocks or even the products such as DT-OS'n 24 34 816 and 25 15 760 contain both polyalkylene glycols and polyaminoamides as building blocks, show an optimal retention performance.

Since the unsatisfactory use function of these products is probably due to "component-location-dependent" reasons of the macromolecule, but this is by no means certain, it would have been expected that the professional community would now take a path other than the aforementioned, which would have suggested Leaving macromolecular compounds with polyalkylene glycol as a building block, because it is known that polyalkylene glycols do not carry any positive or negative charges, which are the prerequisite for good retention agent performance. In fact, therefore, the latest known and relatively best retention products, as described in particular in DT-PS'n 25 02 874 and 25 38 745, no longer contain building blocks in the form of polyalkylene glycol compounds or their derivatives.

In the context of the task of creating even better retention aids, which therefore continues to exist, the solution to this problem according to the invention which follows here is completely unexpected and surprising insofar as, despite that to the person skilled in the art Previously known disadvantageous properties of the polyalkylene glycol building blocks described above have now created a more powerful auxiliary whose composition according to the invention as a building block in turn has polyalkylene glycol compounds and which is characterized in that this auxiliary is a reaction product C which results from the reaction of an aliphatic polyethylene glycol ether amine. as a first partial product A, which is formed by the action of polyvalent aliphatic amines on the reaction product from a polyethylene glycol (as a polydiol building block) with epichlorohydrin, with basic polyaminoamides as a second partial product B known per se from DT-PS 25 02 874 which is formed from at least one polyalkylenepolyamine and / or at least one aminocarboxylic acid or its lactam and / or hexamethylene diammonium adipate, the halogen groups of sub-product A reacting with the -NH - groups of sub-product B with elimination of hydrohalic acids and simultaneous formation of the intermediate AB, is formed so that the intermediate AB obtained is reacted with polyfunctional compounds.

Although products can be used equally well as polyfunctional compounds here, which can be selected, for example, from a group which contains, inter alia, epribromohydrin, epifluorohydrin, the dihaloalkanes, glyoxal-bis-acrylamide, bis-acrylamidoacetic acid, acrylamidoglycolic acid, tetraallyloxyethane and other compounds, epichlorohydrin preferred here.

wobei y und z eine ganze Zahl zwischen 2 und 4, wobei n eine ganze Zahl zwischen 2 und 5 und wobei m eine ganze Zahl zwischen 0 und 5 darstellen, und/oder 0,25 bis 2 Mol eines Amins der allgemeinen Formel

wobei R₁ und R₂ gleiche oder verschiedene Alkylreste der allgemeinen Formel C_xH₂₊₁ oder C_xH_2x- OH sind, bei denen x eine ganze Zahl zwischen 1 und 4 ist, und wobei R₃ Wasserstoff oder ein Alkylrest der allgemeinen Formel C_xH_2x+1 sind, bei denen x eine ganze Zahl zwischen 1 und 4 ist, auf das Umsetzungsprodukt aus 1. Mol des Polyäthylenglykols der allgemeinen Formel

wobei x eine ganze Zahl zwischen 1 und.27 ist, mit 2 Mol Epichlorhydrin gebildet ist, mit 0,5 bis 7 Mol, bezogen auf Polyalkylenpolyamin des basischen Polyaminoamids als dem an sich bekannten zweiten Teilprodukt B, unter anschließender Reaktion des so gebildeten Zwischenprodukts AB mit der polyfunktionellen Verbindung.The other building blocks of the auxiliary according to the invention means can be varied qualitatively and quantitatively without departing from the scope of the invention. Thus, the reaction product C according to the invention can be formed from the reaction of 1 mole, based on polyethylene glycol, of the polyethylene glycol etheramine as the first partial product A, by the action of 0.25 to 1 mole of a polyalkylene polyamine of the general formula

where y and z are an integer between 2 and 4, where n is an integer between 2 and 5 and where m is an integer between 0 and 5, and / or 0.25 to 2 moles of an amine of the general formula

wherein R ₁ and R _{2 are} identical or different alkyl radicals of the general formula C _x H _{2 + 1} or C _x H _2x - OH, in which x is an integer between 1 and 4, and wherein R _{3 is} hydrogen or an alkyl radical of the general Formula C _x H _{2x + 1} , in which x is an integer between 1 and 4, on the reaction product of 1. mol of the polyethylene glycol of the general formula

where x is an integer between 1 and 27, is formed with 2 moles of epichlorohydrin, with 0.5 to 7 moles, based on polyalkylene polyamine of the basic polyaminoamide as the known second partial product B, with subsequent reaction of the intermediate product AB thus formed with the polyfunctional connection.

wobei y und z eine ganze Zahl zwischen 2 und 3, wobei n eine ganze Zahl zwischen 2 und 5 und wobei m eine ganze Zahl zwischen 0 und 3 darstellen, und/oder 0,8 bis 2 Mol eines Amins der allgemeinen Formel

wobei R₁ und R₂ gleiche oder verschiedene Alkylreste der allgemeinen Formel C_XH₂₊₁ oder C_xH_2x - OH sind, bei denen x eine ganze Zahl zwischen 1 und 2 ist, und wobei R₃ Wasserstoff oder ein Alkylrest der allgemeinen Formel C_xH_2x+1 sind, bei denen x eine ganze Zahl zwischen 1 und 2 ist, auf das Umsetzungsprodukt aus 1 Mol des Polyäthylenglykols der allgemeinen Formel

wobei x eine ganze Zahl zwischen 1 und 24 ist, mit 2 Mol Epichlorhydrin gebildet ist, mit 2,5 bis 6,8 Mol,bezogen auf Polyalkylenpolyamin des basischen Polyaminoamids als dem an sich bekannten zweiten Teilprodukt B, unter anschließender Reaktion des so gebildeten Zwischenprodukts AB mit der polyfunktionellen Verbindung gebildet ist. Selbstverständlich ist es im Rahmen der Erfindung je nach Wunsch möglich,zwecks Erhaltung einer ganz bestimmten gewünschten Viskosität des Endprodukts C die zum Schluß der Reaktionsverbindung AB zugesetzte polyfunktionelle Verbindung mengenmäßig entsprechend zu variieren. Auf diese Weise läßt sich das Hilfsmittel in relativ breit gefächerter Form variieren, ohne daß seine besonderen Leistungen verringert werden. Beispielsweise kann man in der vorgenannten Weise Hilfsmittel erhalten, die zum Beispiel in 20 Gew.%iger wässriger Lösung bei 25° C eine Viskosität von einerseits 50 bis andererseits 1000 cp aufweisen.Particularly good results are obtained with an auxiliary according to the invention, the reaction product C from the reaction of 1 mol, based on polyethylene glycol, of the polyethyleneglycol ether amine as the first partial product A, which is caused by the action of 0.7 to 1 mol of a polyalkylene polyamine of the general formula

where y and z are an integer between 2 and 3, where n is an integer between 2 and 5 and where m is an integer between 0 and 3, and / or 0.8 to 2 moles of an amine of the general formula

where R ₁ and R _{2 are} identical or different alkyl radicals of the general formula C _X H _{2 + 1} or C _x H _2x - OH, in which x is an integer between 1 and 2, and wherein R _{3 is} hydrogen or an alkyl radical of the general Formula C _x H _{2x + 1} , in which x is an integer between 1 and 2, on the reaction product of 1 mol of the polyethylene glycol of the general formula

where x is an integer between 1 and 24, is formed with 2 moles of epichlorohydrin, with 2.5 to 6.8 moles, based on polyalkylene polyamine of the basic polyaminoamide as the known second partial product B, with subsequent reaction of the intermediate product thus formed AB is formed with the polyfunctional compound. Of course, it is possible within the scope of the invention, as desired, to vary the quantity of the polyfunctional compound added at the end of the reaction compound AB in order to maintain a very specific desired viscosity of the end product C. In this way, the aid can be varied in a relatively wide range without reducing its special performance. For example, auxiliaries can be obtained in the above-mentioned manner which, for example in 20% by weight aqueous solution at 25 ° C., have a viscosity of 50 to 1000 cp on the one hand.

The above-mentioned qualitative and quantitative variations in the construction of the aid according to the invention ensure that it can be adapted to a wide variety of uses, particularly in the paper-making industry. Since the structure of the partial product B according to the invention already from the older publications DT-PS 25 02 874 and 25 38 745 is known, more will be discussed at this point on the structure of the partial product A according to the invention. In general, unless already mentioned above, it should be noted that the polyethylene glycol ether, which has neither a positive nor a negative charge, is reacted with one mole of epichlorohydrin on each side of its chain molecule with the addition of a special catalyst, such as a boron trifluoro etherate catalyst, and then only on one side of this chain is the epichlorohydrin in turn connected to the special amine of the aforementioned general formulas. This so-called partial product A in the form of its chloropolyethylene glycol ether amine is then combined with the part product B known per se, namely a basic polyamino amide to form a polyethylene glycol ether amine polyamino amide, which is called intermediate AB as mentioned above. This intermediate AB is then reacted once more with a polyfunctional compound selected from the special group of polyfunctional compounds mentioned above, here preferably with epichlorohydrin, so that the end product C is finally in the form of a polyethylene glycol ether-amine-polyaminoamide-epichlorohydrin resin. Although the subject matter of the invention as a product is not limited to a very specific manufacturing process, the subject matter of the invention is to be explained in more detail according to these above, more general procedural instructions, and is thus to be disclosed using the example manufacturing processes.

• 1. Chloridbestimmung
  (Meßmethode, gleichzeitig Erläuterung zu der folgenden Tabelle 2)

The data and numbers given in all the following examples for free chloride, for the amine numbers, for the Viscosity and density are always determined using the same corresponding and following determination method:

• 1. Chloride determination
  (Measurement method, at the same time explanation of the following table 2)

• 2. Die Bestimmung der Aminzahl
  (Meßmethode, gleichzeitig Erläuterung zu der folgenden Tabelle 3)

This takes place according to the well-known titrimetric precipitation method according to F. Mohr. In order to prevent possible complex formation of the silver ion with anions, which can disturb the end point of the titration, the solution to be examined is slightly acidified with acetic acid.

• 2. The determination of the amine number
  (Measurement method, at the same time explanation of the following table 3)

• 3. Die Bestimmung der Viskosität
  (Meßmethode, gleichzeitig Erläuterung zu den folgenden Tabellen 2, 3 und 4)

This is determined by titration of the aqueous resin solution of the above intermediate B, 1 g of resin being dissolved in 100 ml of water, using 0.1 N hydrochloric acid against methyl red. The hydrochloric acid consumed is converted into mg KOH, which is equivalent to 1 g of pure resin, and is thus given in the relevant example table.

• 3. The determination of the viscosity
  (Measurement method, at the same time explanation of the following tables 2, 3 and 4)

This is essentially given for the above-mentioned products A, B and C in the corresponding tables and in a commercially available Höppler viscometer determined at 25 ° C in 20 wt .-% aqueous solutions of the corresponding products (ball No. 4).

4. The determination of density
(Measurement method, at the same time explanation of the following table 4)

This is done by means of a commercially available density meter at 20 ° C in such a way that a standardized hydrometer with shot load settles freely floating in its immersion depth in the 20 ° C warm liquid to be tested. Then you read the value on the lower meniscus of the liquid on the number scale of the hydrometer, which gives the density directly.

The measurement methods that follow when testing the application properties of the product for the purpose of optimally carrying out the process for all the products listed in the examples are carried out under the same conditions and are summarized in tabular overviews 5 to 6. In addition to the products according to the invention taken into account in Tables 1 to 3, other products such as the comparative products designed according to the prior art (Examples 12 to 14) are also taken into account.

5.Determination of the drainage acceleration (measurement method, at the same time explanation of table 5)

The characteristic reduction in grinding degree in oSR is determined according to the specification of leaflet 107 of the Association of Pulp and Paper Chemists and Engineers. Either the inventive and the comparative products are added in these examples as retention agents in the form of their aqueous solutions to the newsprint suspension, the concentration of these aqueous solutions being chosen such that 0.1 or 0.2 g of the retention agent together with 99.8 g or 99.9 g of the atro Ge-Bamt solid constituents of the pulp suspension 100 = wt .-% total solids. Since the numbers for grams correspond to the numbers for% by weight, the amounts of retention agent added are given in% by weight in the above sense in Table 5. The above-mentioned newsprint suspension is obtained by mechanical defibration of commercially available newsprint and subsequent speck-free beating of the defibrated product in a conventional kitchen mixer. The measurements are carried out at a pH of 6.5 and 4.8, which is adjusted with a 1% by weight aqueous alum solution. The fiber concentration is 2g / l water. The 0 sample listed in Table 5 is of course dependent on the choice of waste paper used.

6. Determination of filler retention (at the same time explanation of the following table 6)

Here too, as in Table 5, the same determination method is used both for the examples according to the invention and for the further comparative examples in order to achieve comparable values. Generally he this is followed by the characterization of the filler retention by the ash content of paper sheets, which are produced on the "Rapid-Köthengerät" according to data sheet V / 8/57 of the Association of Pulp and Paper Chemists and Engineers (old version was data sheet 108).

• 80% gebleichter Sulfitzellstoff, (27 °SR); 15% China-Clay; 5% Titandioxid und 0,5% Alaun (bezogen auf atro Papierfaser). Die Stoffdichte der Papierblätter zeigte ≙ 0,24 g/l Wasser; der pH-Wert der aus dem Papierblatt durch Einbringen in Wasser herstellbaren Fasersuspension beträgt 6,2. Der Retentionsmittelzusatz bei der Stoffaufbereitung beträgt 0,02 Gew.-%,bezogen auf Atro-Retentionsmittel bzw. auf Atro-Papierfaserstoff.

The aforementioned paper sheet, which is used to determine the retention performance of the respective comparison products, has the following composition of matter:

• 80% bleached sulfite pulp, (27 ° SR); 15% china clay; 5% titanium dioxide and 0.5% alum (based on dry paper fiber). The consistency of the paper sheets showed ≙ 0.24 g / l water; the pH of the fiber suspension that can be produced from the paper sheet by introducing it into water is 6.2. The retention agent additive in the stock preparation is 0.02% by weight, based on the atro retention agent or on the atro paper pulp.

The ash contents given in Table 6 are percentages by weight.

The individual examples now follow, examples 1a, 1b and 1c being shown in detail, whereas the following further examples, since they are carried out under the same process conditions as examples 1a, 1b and 1c, are listed in abbreviated form in tabular form. For complete The following text examples 1a, 1b and 1c are also included in the overview table for an overview of the entire sample material listed here.

For reasons of space, the substance names fully written out in text examples 1a, 1b and 1c are only listed in the following table series in the form of their abbreviations.Therefore, an explanation of the short names used in the following table series for the chemical starting products with the addition of some follows Information on their concentration or on the medium in which they are dissolved.

• 1st EP:
  • Epichlorohydrin, density 1.18.g. cm ^-1 ; is always available as a 98% by weight solution.
• 2. DTRA:
  • Diethylenetriamine, is present as a 100% by weight pure substance.
• 3. Polydiol:
  • Polyethylene glycol ether is present as the pure substance, the number added in the table indicates the average molecular weight of this compound, for example 400; 600; 1000; 6000 etc.
• 4. BF ₃ etherate:
  • Börtrifluorid etherate of the empirical formula C ₄ H ₁₀ BF ₃ O; is always available as a 65% by weight solution.
• 5th PA:
  • Polyaminoamide resin solution which contains the secondary amines as a reactive group. 1 mole of this compound corresponds to 1NH.
• 6.AS:
  • Adipic acid is present as a 100% by weight solid.
• 7. CL:
  • Caprolactam, is present as a 100% by weight solid.
• 8. AH-S:
  • Salt from adipic acid and hexamethylenediamine is present as a 100% solid.
• 9th DAM:
  • Diethanolamine is always present as a 100% by weight substance.
• 10. TMA:
  • Trimethylamine, is always available as a 45% by weight aqueous solution.
• 11. DMA:
  • Dimethylamine, is always available as a 40% by weight aqueous solution.

In order to further explain the following series of examples, it should be said in explanatory terms regarding the tabular compilations listed there that in Table 1 the partial products A according to the invention, which always contain the same molar amount, but Polgdiolen but with different molecular weight, with twice the molar amount be implemented on epichlorohydrin. Diethylenetriamine (DTRA), dimethylamine (DMA), trimethylamine (TMA) and diethanolamine (DÄAM) were used as the amine component. The intermediate analysis values of sub-products A are then listed after Table 1. Table 2-. summarized.

It can be seen from Table 3 that the intermediate product B in the relevant examples 1b to 3b always contains the same amounts of adipic acid (AS) and diethylenetriamine (DTRA). In Example 1b, Caprol ^p ctam (CL) was also used, and in Example 3b the salt of adipic acid and hexamethylene diamine (hexamethylene diammonium adipate; AH-S) was also used.

As can be seen from the following Table 4, the ratio of partial product A to partial product B was set to 1 to 3.33 in the preparation of the end products C. Only in Example 11c, which is also in this table, was the above ratio changed and set to 1 in 6.65.

• Beispiel 12 entspricht dem Beispiel 1 aus der DT-PS 17 71 814;
• Beispiel 13 entspricht dem Beispiel 1 aus der DT-OS 23 53 430;
• Beispiel 14 entspricht dem Beispiel 1 aus der DT-PS 25 02 874.

Table 5 shows the dewatering acceleration, measured in oSR, whereby in example 10c the influence of the very high molecular weight polydiol with an average molecular weight of 6000 already shows itself insofar as this results in a less severe reduction in the degree of grinding compared to the examples according to the invention. Thus, although the invention was carried out qualitatively, a polydiol with a molecular weight of 6000 was used quantitatively, namely instead of using polydiols with average molecular weights 400 and 1000 which are only suitable for the invention. This leads to such bad results that they show no improvement compared to the prior art. Accordingly, Table 5 thus teaches, inter alia, that polydiols with an average molecular weight which are preferably not higher than about 1200 should be used if the products are constructed according to the invention and accordingly also have to have an excellent retention or drainage performance. The example, the polydiol building block of which has an average molecular weight of 6000, can therefore be counted among the comparative examples which are now briefly discussed below. As a further comparative example, example 1b ¹ listed in table 4 is to be evaluated. It is intended to show that without the incorporation of the partial product A according to the invention, that is to say only when the known intermediate B is crosslinked with epichlorohydrin, the resultant aid for improving the retention, drainage and dilatation provides only significantly poorer retention, drainage and flocculation values than products which according to the examples of the invention have been prepared. Table 5 also contains further examples according to the invention, which are taken from the most important prior art publications:

• Example 12 corresponds to Example 1 from DT-PS 17 71 814;
• Example 13 corresponds to Example 1 from DT-OS 23 53 430;
• Example 14 corresponds to Example 1 from DT-PS 25 02 874.

As already explained above, the comparison of the examples according to the invention with the prior art examples for the product application according to Table 5 proves that the products according to the invention are significantly superior to previously known products in terms of drainage acceleration. In the same sense, the comparison of the filler retention performance of the corresponding products shown in Table 6 should also be interpreted.

The individual examples now follow:

example 1 1a) Production of sub-product A.

In a 4 liter glass round bottom flask equipped with a commercially available anchor stirrer, a thermometer, a reflux condenser and an inlet funnel, 160 g of polyethylene glycol ether with an average molecular weight of 400 corresponding to 0.4 moles are placed in front and with 2 ml of the boron trifluoride etherate catalyst solution (Catalyst molecular formula: C ₄ H ₁₀ BF ₃ O) mixed. This mixture is heated to 60 ° C. with the aid of a water bath and the polydiol in the mixture is reacted with slowly added 75.5 g of epichlorohydrin, corresponding to 0.8 moles. The reaction takes place at a reaction temperature of at most 65 ° C in a time of 2.5 hours in the form of an addition reaction. The resulting product, namely polyethylene glycol-bis-β-hydroxy-α-chloropropyl ether, is now added with 35.4 g DTRA, corresponding to 0.336 moles, after adding 271.7 ml deionized water, which is stirred in at 65 ° C. in two minutes moved an inlet funnel. During the reaction between the DTRA and the intermediate mentioned above, the temperature is adjusted if necessary

Water cooling kept at 65 ° C. After an hour, the reaction solution temperature drops due to the completion of the reaction between the aforementioned substances. Sub-product A (β-hydroxy-α-chloropropylpolyethylene glycol ether-β-hydroxy-α-propylamine) obtained in this way gave the following values during its analysis:

1b) Production of sub-product B.

In a pressure vessel designed as a steel autoclave with a stirrer, a temperature sensor in the form of a thermal sensor and a distillation condenser, 1,460.2 g of adipic acid (100% by weight, corresponding to 10 mol of solid); 1,124.5 g of diethylene triamine (100% by weight, corresponding to 10.9 mol; liquid) and 226.34 g of caprolactam (100% by weight, corresponding to 2 mol; solid) were introduced in the form of their pure substances. After overlaying the above-mentioned filling material with oxygen-free nitrogen, which thus replaces the supernatant residual gas mixture, the contents of the vessel are heated to 160 ° C. after the end of the reaction vessel and left at this temperature for 30 minutes with stirring. The water of reaction released is then distilled off (a total of 360 ml, corresponding to 100% of theory). The reaction mixture, which is now free of condensation, is then further heated to 180 ° C. and stirred at this temperature for a further two hours.

The mixture reacts further, nitrogen being continuously passed through the condensing reaction mass.

After the resulting polycondensate melt has been cooled to 135 ° C., a total of 2,553 ml of water are added, while the substance is cooled further. The resulting aqueous polyamino amide resin solution is now examined and shows the following test result values:

1c) Preparation of the final product C

543.4 g of the 50% by weight partial product A corresponding to 0.4 mole, based on polydiol 400 in the form of the β-hydroxy-α-chloropropyl-polyethyleneglycol ether, are placed in the 4 liter glass round bottom flask already described in Example 1a above. β-hydroxy-α-prop3rlamine first mixed with the same amount by weight of water, so that a 25 wt .-% solution is formed.

For this purpose, 624.4 g of a 48% strength by weight solution of partial product B, as has been prepared in a known manner in Example 1b above, in the form of the basic polyaminoamide resin solution, and the whole is then added with 574.4 g of water with stirring transferred. Then continue under set stirring the aforementioned vessel contents heated to 80 ° C within two hours, the halogen group of sub-product A reacting with the -NH groupings of sub-product B with elimination of hydrohalic acid to form intermediate AB. As soon as the product AB is formed, 11.35 ml of epichlorohydrin as 98% by weight product with a density of 1.18 g. cm ^-3 metered into the vessel contents while maintaining the above-mentioned temperature. After a reaction time of 7.5 hours between the above-mentioned intermediate AB and the epichlorohydrin supplied to it, the reaction-related increase in viscosity practically ceases, with the result that the end product C is formed in the form of a highly viscous clear solution of polyethylene glycol ether-amine-polyamino-amide-epichlorohydrin resin. The examination of the above end product C according to the invention showed the following values:

As already stated above, the following further examples, summarized in the following tables, are carried out in the same manner as given for the above examples 1a, 1b and 1c, under the same process conditions. As already mentioned, the text examples 1a, 1b and 1c above are summarized in the following tables for the sake of clarity.

The auxiliary according to the invention for improving the retention of washable solids, for accelerating the dewatering of suspensions and for the faster treatment of industrial waters, wastewater and sludges by adding basic water-soluble polymers as an aqueous polymer solution is admittedly possible Mainly used advantageously in the paper industry, but at the same time it is also very well suited for the treatment of industrial water, waste water purification and sludge conditioning in other branches of industry. The term "sludge treatment" falls. the preparation of fresh sludge and activated sludge, as well as the sludge thickening and sludge flotation processes known per se, in which the aid according to the invention can be used very well. It is very advantageous here that these auxiliaries, for example in the clarification process, are insensitive to the addition of a number of different substances, which is why it is readily possible, for example inorganic flocculants, such as those based on aluminum and iron salts or on the base of lime compounds are commercially available, without the auxiliary properties of the invention being adversely affected in terms of their use properties.

If the aid according to the invention is used in sedimentation and clarification tanks, its use in an amount of about 0.1 to 4 mg per liter of the substance to be clarified is recommended.

In other cases, for example in the conditioning of waste water sludges, in dewatering in dry gels or in the use of mechanical processes such as centrifugation, the water can be removed from the sludge better and more quickly if the auxiliary according to the invention is used in amounts of about 2 to 12 kg per ton of dry sludge is added to the substance to be treated.

If the sludge to be treated is to be stabilized, it is expedient to add about 50 to 150 mg of the auxiliary according to the invention to the sludge per corresponding unit quantity. The stabilization advantageously occurs by promoting the formation of tear-resistant flakes by the aid.

In the context of the papermaking to be cited as the most important field of use for the auxiliary according to the invention, the said auxiliary can of course not only be added separately, but also in admixture with the other substances required in papermaking, such as dyes, antioxidants, optical brighteners and fluorescent agents, c the aid is not sensitive to these substances. In practice, the aforementioned additional method of prior mixing of the additives is often used because in general, for example, optical brighteners and fluorescent agents are only required in small quantities in the paper in order to achieve the desired change in the appearance of the paper.

Further areas of application of the aid according to the invention in the context of paper manufacture relate to the advantageous performance of the agent in achieving good shear stability, which is important if, for example, pumps, vibrating sieves and other devices are used in paper manufacture.

In addition to papermaking, the auxiliary according to the invention can of course also be used in completely different areas than those mentioned above. As a hair fixative or to anchor yourself Hydrophobic coating agents, which are applied in the form of aqueous dispersions or other solutions, for example to carrier substances such as fabrics of all types, can be used as well as an improver for the wet strength of fabrics (especially paper), but in the latter case advantageously after acidification of the agent.

In general, the auxiliary according to the invention is very stable in storage even in the basic medium if, as the person skilled in the art knows, only as much crosslinking agent as required is added in the preparation of the crosslinking agent, for example using epichlorohydrin.

If the crosslinking agent is added in an unusual or unintentional manner, the agent can still be used, but must be used to achieve a suitable storage stability, which also prevents any gelation that might otherwise occur.

Claims (5)

1. Aid for improving the retention of washable solids, for accelerating dewatering of suspensions and for the faster treatment of industrial water, waste water and sludge by adding basic water-soluble polymers as an aqueous polymer solution, characterized in that the aid is a reaction product C, which results from the reaction of a aliphatic polyethylene glycol etheramine as a first partial product A, which is formed by the action of polyvalent aliphatic amines on the reaction product from a polyethylene glycol with epichlorohydrin, with basic polyaminoamides as a known second partial product B, which consists of at least one polyalkylene polyamine and / or at least one aminocarboxylic acid or whose lactam and / or hexamethylene diammonium adipate is formed, the halogen groups of sub-product A with the -NH groupings of sub-product B with elimination of hydrohalic acids by means of Bi Solution of the intermediate 'AB react so that the intermediate AB obtained is reacted with polyfunctional compounds. 2. Aid according to claim 1, characterized in that the polyfunctional compound is epichlorohydrin. 3. Aid according to claims 1 and 2, characterized in that the reaction product C from the reaction of 1 mol, based on polyethylene glycol, of the polyethylene glycol etheramine as the first partial product A, which by the action of o, 25 to 1 mol of a polyalkylene polyamine of the general formula

where y and z are an integer between 2 and 4, where n is an integer between 2 and 5 and where m is an integer between 0 and 5, and / or 0.25 to 2 moles of an amine of the general formula

wherein R1 and R _{2 are} identical or different alkyl radicals of the general formula C _x H _{2 + 1} or C _X H _2X - OH, in which x is an integer between 1 and 4, and wherein R _{3 is} hydrogen or an alkyl radical of the general formula C _x H _{2x + 1} , where x is an integer between 1 and 4,
on the reaction product from 1 mole of the polyethylene glycol of the general formula

where x is an integer between 1 and 27, is formed with 2 moles of epichlorohydrin, with 0.5 to 7 moles, based on polyalkylene polyamine, of the basic polyamino amide as the second part B known per se, with subsequent reaction of the intermediate AF thus formed is formed with the polyfunctional compound. 4. Aid according to claims 1 to 3, characterized in that the reaction product C from the reaction of 1 mole, based on polyethylene glycol, of the polyethylene glycol etheramine as the first partial product A, which by the action of 0.7 to 1 mole of a polyalkylene polyamine of the general formula

where y and z are an integer between 2 and 3, where n is an integer between 2 and 5 and where m is an integer between 0 and 3,
and / or 0.8 to 2 moles of an amine of the general formula

where R ₁ and R _{2 are the} same or different alkyl radicals general formula C _x H _{2 + 1} or C _x H _2x ―OH, in which x is a. is an integer between 1 and 2, and where R _{3 is} hydrogen or an alkyl radical of the general formula C _x H _{2x + 1} , in which x is an integer between 1 and 2,
on the reaction product from 1 mole of the polyethylene glycol of the general formula

where x is an integer between 1 and 24, is formed with 2 moles of epichlorohydrin, with 2.5 to 6.8 moles, based on polyalkylene polyamine, of the basic polyamino amide as the known second partial product B, with subsequent reaction of the thus formed Intermediate AB is formed with the polyfunctional compound. 5. Use of the aid according to claims 1 to 4 in the paper manufacturing industry.