FI61904B - CONDITIONING FOR CONFIRMATION OF CONTAINERS - Google Patents

Description

I- —Ί Γ-, ADVERTISING

jjäTg Μ O1) UTLÄGGNINGSSKRIFT 61904 («)

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/ (51) 69/48, d 21 H 3/58 ENGLISH I—> FI N LAN D (21) P * t * nttlh »k« mui - Ptt * nt »n * öknlng 752009 (22) Htktmlspilvi - Ansöknlngtdag 10.07 -75 (Fl) (23) Alkupllvl —Glltlghetsdag 10.07-75 (41) Tullut JulklMksI - Bllvlt offontlig 20.01.76

National Board of Patents and Registration (44) Date of publication and date of issue. -

Patent · och regitterstyrelsen Ansökan utlsgd och uti.skrifun publkerad 30.06.82

(32) (33) (31) Privilege claimed —Begird prlorltet 19.07.7U

10.0l.75 Federal Republic of Germany-Förbunds-republiken Tyskland (DE) P 2L3L816.I

p 2515760.2 '(71) BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany-Förbunds- republiken lyskland (DE) (72) Emil Scharf, Ludwigshafen, Rolf Fikentscher, Ludwigshafen,

Werner Auhorn, Frankenthal, Werner Streit, Ludwigshafen, Federal Republic of Germany-Förbundsrepubliken lyskland (DE) (7 ^) Oy Kolster Ab (5 * 0 Method for the production of nitrogen-containing condensation products -Förfarande för framställning av kvävehaltiga kondensations

The invention relates to a process for the preparation of condensation products of novel polyamidoamines and high molecular weight bifunctional crosslinking agents. The condensation products prepared according to the invention have particular use as retention and dewatering aids in the paper industry.

It is known that polyethyleneimine and, to a lesser extent, polypropyleneimine are used in papermaking as filler and fiber retention aids, as a dewatering accelerator in web formation and as a flocculant in fiber recovery. Such products have been known for over 30 years. A step forward in development was the use of epichlorohydrin as a crosslinking agent, whereby crosslinked polyethyleneimines are known, which are known, for example, from DE patent 1 670 296. In addition, it is also known that by crosslinking polyamidoamines, i. reaction products of polyamines and dicarboxylic acids, for example epichloro-2 61 904 hydrin, good retention aids for papermaking are obtained. However, from a technical point of view, these product groups have the disadvantage that they individually have an optimum effect only in a limited pH range. Thus, for example, the crosslinked polyamines according to DE patent 1,670,296 are optimal only in the neutral range, the crosslinked polyamidoamines known from U.S. Pat. No. 3,250,664 only in the acidic pH range.

In papermaking, depending on the quality of the paper, the manufacturing conditions sometimes vary very rapidly between acidic and neutral, so there has long been a need to develop an excipient that is optimally effective in both neutral and acidic regions.

According to DE-A-1 802 435, this problem is solved by first grafting ethyleneimine into the polyamidoamine and crosslinking the product obtained with epichlorohydrin. These excipients have so far been completely satisfactory. A disadvantage, however, which does not affect the quality of the paper obtained is the dangerousness of the monomeric ethyleneimine required in the manufacture, which the compound is known to force due to its increased caution due to its toxicity. Moreover, this compound is not available to such an extent that the method described in said patent publication could be used everywhere without restriction. Economic considerations led to the establishment of the object underlying the present invention, namely to find papermaking aids which use no or little monomeric ethyleneimine and which nevertheless have the same, if not even better, effects in papermaking.

The increasing demand of papermakers for process rationalization, which includes, above all, process acceleration, also led to the object of the invention, the creation of new excipients which accelerate dewatering compared to the excipients of the latter literature,

3 61904

At the same time, however, the originally posed problem of the suitability of the excipient in the acidic and neutral range has been solved. In addition to avoiding the use of monomeric ethyleneimine, the invention also achieves improvements that speed up papermaking and thus make it more economical.

The invention relates to a process for the preparation of nitrogen-containing condensation products by the reaction of polyamidoamines with a crosslinking agent, which polyamidoamines are prepared from 1 molar part of C 1 -C 4 dicarboxylic acid and from 0.8 to 1.4 molar parts of 3 to 10 basic nitrogen atoms per molecule of polyalkylene. polyamine, optionally containing up to 10% by weight of diamine, grafted with 2 to 8 ethyleneimine units per basic nitrogen group, characterized in that one part by weight of said polyamidoamine is reacted at 20 to 100 ° C , 3 to 2 parts by weight of a polyalkylene oxide containing 8 to 100 alkylene oxide units, the terminal H-groups of which have been reacted with at least an equivalent amount of epichlorohydrin, the reaction being allowed to proceed until a high molecular weight, still water-soluble resin is obtained. the viscosity measured at 20 ° C in a 20% aqueous solution is greater than 300 mPa.s.

The reaction of the reaction products of epichlorohydrin and polyalkylene oxide derivatives with nitrogen-containing compounds is known from DE-A-1 932 394 as well as from U.S. Pat. No. 3,691,110 and U.S. Pat. No. 3,215,654. Even more complicated reactions using bifunctional crosslinking agents are described in DE-A-2 162 567 as retention aids useful in the paper industry. In addition, in order to develop their full efficiency, the condensation products obtained according to these three references must either be subsequently crosslinked with epichlorohydride or converted into a water-soluble form with sodium bisulphate. The latter measure is the subject of the teachings of U.S. Patent 3,691,110.

H 61904 The principle of this reaction is also apparent from DE 1 546 290. However, it does not react with bifunctional polyalkylene oxide derivatives to polyamidoamines, but exclusively to polyalkylene polyamines, in particular low-molecular polyalkylene polyamines. According to the literature, the obtained products can be used as auxiliaries in the recovery of fibers and fillers from paper machine wastewater. These agents are not very suitable as fiber retention agents or dewatering accelerators, their use is again limited by a narrow pH range. The process according to the invention, which is based on the use of polyamidoamines, certain weight and molar ratios and, above all, on the monitoring of the final viscosity, to obtain new products with optimal effect, thus represents a clear technical advance compared to the prior art.

The polyalkylene polyamines used as starting materials in the process according to the invention are known compounds which are commercially available and which can generally be prepared by condensing the corresponding alkenyldiamines. Also in the synthesis of ethylenediamine, they are obtained as by-products and can be easily obtained by hydrogenation of acrylonitrile addition products.

Suitable polyalkylene polyamines are those which contain 2 to 6 alkylene bridges between the amino groups. Suitably those having 3 to 10 basic nitrogen atoms in the molecule are used. Examples are polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenetrentamine, dipropylenetriamine or tripropylenetetramine such as dihexamethylenetriamine. Polyalkylene polyamines can also be used as raw materials or mixtures, possibly with small amounts of diamine. The diamines, mainly ethylenediamine, are preferably present in an amount of up to 10% by weight.

Dicarboxylic acids condensable with polyalkylene polyamines are those having 4 to 10 carbon atoms, such as succinic acid, maleic acid, adoptic acid, glutaric acid, cork acid, sebacic acid or tetraphthalic acid. Generally, 0.8 to 1.4 mole parts of polyamine are used per mole of dicarboxylic acid. According to DE-A-1 802 435, the reaction products can be inoculated with 2 to 8 moles of ethyleneimine per basic nitrogen atom group.

The second reactant is a polyalkylene oxide derivative whose OH groups at the terminal position have been reacted with epichlorohydrin. Suitable polyalkylene oxide derivatives are generally compounds which, before the reaction, contain from 8 to 100 alkylene oxide units in the polyalkylene oxide chain. Suitable polyalkylene oxides are mainly ethylene oxide and / or propylene oxide homopolymers or copolymers, "in which case the proportion of propylene oxide groups should expediently be at most 50% of the total number of alkylene oxide groups. block polymers in which R 1 represents an ethylene radical, R represents a 1,2-propylene radical, m or p values from 4 to 50, n values from Q to 50, and A represents a dihydric alcohol radical having from 2 to 6 carbon atoms, or a polypropylene glycol radical having 1 to 5 ° propylene units, provided that in this case n is equal to 0. Individual representatives are thus oxyethylated or oxyethylated-oxypropylated dihydric alcohols, such as glycol, propylene glycol, polyalkylene, up to 50 propylene units in the molecule. block copolymers of ethylene and propylene oxides on both sides. Polyoxyethylated or optionally oxypropylated products are thus compounds having two free hydroxyl groups at the terminal position. These terminal hydroxyl groups are reactive centers in the subsequent reaction with epichlorohydrin. In this case, at least an equivalent amount, preferably 1.1 to 1.5 moles of epichlorohydrin, of β 61904 is used for the OH groups. The result is β-hydroxy-γ-chloropropyl ether compounds, which on cleavage of HCl give glycidyl ethers. These compounds actually act as crosslinkers for polyamidoamines, and are hereinafter also referred to as crosslinking agents.

The reaction of epichlorohydrin with polyalkylene oxide derivatives takes place according to known reaction mechanisms and is initiated by Lewis acids. Examples of suitable Lewis acids are boron fluoride etherate, phosphoric acid, perchloric acid, chloroacetic acid, aromatic sulfonic acids, zinc chloride or aluminum fluoride. But in general, it is appropriate to use boron fluoride etherate as a catalyst (Lewis acid) in the reaction.

The high molecular weight bifunctional crosslinking agents are then reacted with polyamidoamines, using 0.3 -? Per part by weight of polyamidoamine. parts by weight of crosslinking agent. The amount of bifunctional compound required for crosslinking will, of course, depend on the structure of the polyamidoamine and crosslinking agent used. When high molecular weight crosslinking agents are used to crosslink a particular polyamidoamine to prepare a solution of the desired viscosity, the higher the crosslinking agent, the higher the reaction temperature and the higher the water content of the solution.

The crosslinking agent is used in the amounts mentioned above, in particular 0.35 to 1.8 parts by weight per part by weight of polyamidoamine. The crosslinking reaction is expediently carried out in a solution of 5 to 50%, in particular 10 to 30% by weight, based on the sum of the weights of the reactants. The reaction can also be carried out by adding the amount of crosslinking agent required for the desired crosslinking, either at once or in portions. The progress of the reaction can be monitored by observing an increase in the viscosity of the aqueous solution. The latter procedure must always be preferred, since in this case the reaction can be better controlled and the risk of the reaction mixture coagulating is substantially lower. In addition, with the addition of high molecular weight crosslinking agent doses, overdose can be avoided and a certain viscosity can be easily adjusted. The reaction is allowed to continue until further water-soluble high molecular weight resins having a viscosity of> 300 mPas measured at 20 ° C in a 20% aqueous solution are obtained. The main aim is to prepare resins with a viscosity of 400-2500 mPas. The reaction is generally carried out at a temperature of 20 to 100 ° C, especially 40 to 80 ° C for 1 to 15 hours. The condensation reaction is conveniently carried out at a pH above 8, preferably between pH 9-11.

According to a particularly preferred embodiment of the invention, only a part of the discontinuous polyamidoamine and the polyalkylene oxide derivative is first condensed by stirring aqueous solutions of the starting materials in a suitable reaction vessel and then heating the mixture to a higher temperature, for example 50 ° C to 70 ° C. The condensation is then carried out to such an extent that the viscosity measured at 20 ° C in a 20% aqueous solution is approximately 50-500, in particular 150-300 mPas. As usual, good mixing of the substances is ensured throughout the condensation.

Aqueous solutions of polyamidoamine and polyalkylene oxide are then added to the condensation product, which has not yet needed to achieve the desired viscosity. Preferably, however, the starting materials are already condensed to the desired viscosity.)

The addition of the mixture is preferably carried out continuously, but can also be carried out intermittently, and is continued in order to achieve the highest possible volume-time yield until the reaction vessel is about 90% full. The temperature of the aqueous mixture of reaction components should not exceed 4 ° C where possible. Generally, the temperature is at or below room temperature.

The total amounts of polyamidoamine and polyalkylene oxide, based on the discontinuous, are first condensed up to 90% by weight, in particular up to 60% by weight, and then the residual starting material is fed continuously or intermittently to the discontinuous condensation product. The mixture ratio of polyamidoamine and polyalkylene oxide is adjusted according to the viscosity of the condensate in the reaction vessel. At the beginning of the continuous or intermittent addition of the mixture, the content of crosslinking agent is, for example, 70% by weight, and is reduced to 25% by weight continuously or stepwise by the end of the addition. For this, standard equipment in the technology can be used. For example, aqueous solutions of both components are fed to the mixer, from which the mixture is continuously pumped into the condensing vessel, by means of metering pumps, whereby the supply of crosslinking agent is reduced as the condensation progresses.

If the viscosity of the substance in the condensing vessel during condensation deviates from a suitable range, the viscosity of the condensation product can be adjusted as desired by the control equipment by lowering the amount of crosslinking agent in the fed mixture.

With this procedure, the viscosity of the condensation product can be precisely adjusted and the polymerization time can be shortened. An additional method-technical advantage is that the process flow can be controlled completely automatically, in contrast to a purely discontinuous method.

The condensation products prepared according to the invention are basic due to the amino groups they contain. However, their effectiveness as dehydrating, flocculating and retention aids is not affected by neutralization. Compared to products consisting of basic crosslinked polyamidoamines or crosslinked 1,2-polyalkylene polyamines and epichlorohydrin alone, they have better performance in the paper industry in filler retention, dewatering acceleration and flocculation or foaming recovery. Compared to the results obtained with the products according to DE-A-1 802 435, these effects are often better. In particular, the improved degree of whiteness of the papers obtained still needs to be emphasized, as the papers are also less prone to yellowing during long-term storage. These products can be used in any pH range present in papermaking. The products according to DE 1 546 29Q are only suitable for use as blowing agents for paper machine effluents, while the products according to the invention are generally useful.

The products made according to the invention can be successfully added in the production of all kinds of papers in amounts of about Q, 1 to Q, 3% by weight based on the weight of the cellulosic fibers in the fiber suspension, in the production of glued and non-glued glossy boards with and without aluminum sulphate.

, 61904

The parts and percentages mentioned in the following examples are by weight.

Examples A) Preparation of polyethylene glycol ether bis- [3-hydroxy-N-chloropropyl ether ("Parts" are parts by weight) I part of a polyethylene glycol ether containing on average an ethylene oxide unit per molecular weight According to K. Fischer, (v) part of epichlorohydrin is mixed, <(1) part of boron fluoride diethyl etherate is added to the mixture and then at 60-70 ° C an additional part of epichlorohydrin is added over 0.5-1.5 hours; post-condensed at 60-70 ° C until the epoxy titer of the solution reaches zero in e). The chlorohydrin content of the product obtained is chosen / g. (Boil for 30 minutes for 0,1 min

With NaOH, back-titrated to an acid content of X millivals / g).

Koe 1 Koe 2 Koe 3 Koe 4 Koe 5

Polyethylene glycol / epichlorohydrin molar ratio 1: 3.0 1: 2.2 1: 3.0 1: 2.6 1: 3.0 I 3312 4050 4050 4542 4774 II 9 18 18 34 90 III 266 136 145 83, 5 29 IV 0.10 0.22 0.017 0.03 0.04 V 222 102 139 72 33 VI 6.6 8.1 8.1 9.1 12.0 VII 1998 916 1148 650 300 VIII 3.2 4, 0 5.7 5 4 IX 3.52 2.00 2.24 1.33 0.54 X 0.0097 0.0085 0.006 0.008 0.013 B) Preparation of polyamidoamines

Experiment 6 (glutaric acid-diethylenetriamine) 0 61 904 660 parts of glutaric acid are added under a nitrogen atmosphere for 20 min. 566.6 parts (1: 1.1 molar ratio) of diethylenetriamine. The temperature of the reaction mixture then rises to about 130 ° C. The temperature of the reaction melt rises to 158-160 ° C in about two hours and to 170 ° C within a further hour, and the water formed during the condensation is distilled off (172 parts of distillate).

After 2.5 hours, at a temperature of 170 ° C at the bottom of the apparatus, the acid number of the resin has dropped to 5.5, then cooled and, starting at 150 ° C, 1040 parts of water are slowly added. The slightly colored aqueous resin solution has the following properties: water content (K. Fischer) 49% acid number 3.54 amine number teared with perchloric acid in glacial acetic acid: 4.05 millivalents / g viscosity ^ 5%, 20 ° C (Höppler's ball drop method)

196 cP

Experiment 7 (Adipic acid-diethylenetriamine) 1044 parts of water and 2150 parts of diethylenetriamine are mixed together under nitrogen at room temperature and then 2800 parts of adipic acid are added under cooling below 80 ° C. Within 5 hours, the added water formed in the condensation is distilled off by heating the lower part of the apparatus to 170 ° C and kept at this temperature until the acid value of the resin is less than 10 (9.8), (about 10 hours at 170 ° C) then cooled and 130- From 140 ° C, a further 3100 parts of water are added to the viscous resin. The aqueous solution of the resin has the following properties: water content (K.Fischer): 38.6% (solids 61.4%) acid number: 10.3 calculated on 100% of the product amine content (circulating in glacial acetic acid with perchloric acid) 5.3 millivalents / g of 100% product viscosity (45%, Höppler ball drop method) 202 cp

Experiment 8 (adipic acid-dipropylene triamine) 585 parts of dipropylene triamine dissolved in 300 parts of water are mixed with 584 parts of adipic acid (under a nitrogen atmosphere), whereby the aqueous solution is heated to about 120 ° C. During five hours, the condensation temperature is raised to 150 ° C, then within two hours to 165-170 ° C and maintained at this temperature for 9 hours. The bases, which had distilled off about 61,904, were supplemented in the last 9 hours by adding an additional 67 parts of dipropylene triamine. The acid number of the resin after condensation was 9.2. The resin was cooled and from 130 ° it was mixed with 440 parts of water.

Solids content (Heidbrink *: 0.3 g; 60 min. 80 ° C): 69.4% amine number: 3.94 millivalents / g acid number: 8.6 viscosity as a 45% aqueous solution at 20 ° C (Höppler ball drop viscometer) 300 cP n ^ °: 1.4259 (45%)

Experiment 9 (adipic acid methyl ester + dipropylene triamine) 585 parts of dipropylene triamine are mixed at 80-85 ° C (nitrogen atmosphere) with 696 parts of adipic acid dimethyl ester. For amide formation, the temperature of the bottom of the apparatus is raised to 168-170 ° C in five hours and the methanol formed is distilled off. After a further two hours at 168-170 ° C, 252 parts of distillate have formed. The viscous resin is cooled and mixed with about 1000 parts of water: water content (K. Fischer): 48.6% solids content (Heidbrink, see Experiment 8): 50.9 u amine content (titrated in glacial acetic acid with HClO 2): 2.96 millivalals / g viscosity as 45% aqueous solution (20 ° C, Höppler ball drop method): 151 cP nj ^ (45%) 1.4259

Experiments 10 / (11) (adipic acid + tetraethylenepentamine (+ ethylenediamine) Dissolve 692 parts of tetraethylenepentamine (529 parts of tetramethylenepentamine and 113 parts of ethylenediamine) in 300 (400) parts of water and mix with 438 (584) parts of adipic acid. above 100 ° C. As the water distills off, the temperature at the bottom of the apparatus rises to 160-170 ° C and is maintained at this temperature for about 7 hours.During the condensation, 383 parts (540 parts) of distillate containing 0.78 (1.34) millivalence / g of amine The condensation of the resin was stopped when the acid number was 10.0 (10.7), cooled and diluted at 140 ° C with 1000 parts (1050 parts) of water: *) Fette und Seifen 53, (5), 1951 page 291 12 61 904

Experiment 10 Experiment 11 water content (K. Fischer) 49.9% 50.4% solids content (Heidbrink) 50.2% 49.9% amine content 5.65 mval / q 4.10 mval / g acid content 0.088 mval / g 0.096 mval / g

viscosity (45 %- 721 cP 882 cP

20 ° C, Höppler ball drop method)

Experiment 12 (adipic acid + diethylenetriamine-hexamethylene diaminadipate ("AH salt")) To 458 parts of diethylenetriamine and 458 parts of water are added 548 parts of adipic acid and 204 parts of AH salt under a nitrogen atmosphere and raised at about 120 ° for 5-6 hours. bottom temperature of the equipment to 165-175 ° C. During the next 8 hours of condensation at about 170 ° C, the acid number of the resin drops to 9.9. The distillate obtained (642 parts) contains 0.103 base equivalents. The black-colored viscous resin is cooled and diluted from 140 ° C with 1100 parts of water: water content (K. Fischer): 51.2% solids (Heidbrink): 48.6% amine content: 2.4 mval / g acid content: 0.068 mval / g

viscosity (20 ° C, 45% aqueous solution, Höppler ball drop method) 1 + 2 2 cP

2 0 (45%) 1.4234

Experiments 13/14 (according to DE-A-1 1 80 2 43 5) 326 parts of the 61.4% resin obtained in experiment 7 are mixed with 50 (70) parts of 4.5 parts of concentrated sulfuric acid and heated to 80 ° C. 800 (200) parts of a 50% aqueous solution of ethyleneimine are added over 4-5 hours with good stirring and then the temperature of the resin solution is maintained at 80-90 ° C for a further 2-3 hours (until the aziridine ring can no longer be detected with p-nitrobenzylpyridine). The product features are: 13 61 904

Experiment 13 Experiment 14 water content (K. Fischer) 48.4% 49.2% (active ingredient content): (51.6% 50.8%) amine content (titrated 7.1 mval / g 5.2 mval / g in glacial acetic acid with perchloric acid) 20 ηβ as a 45% aqueous solution 1.4389 1.3229 viscosity (20 ° C, 45%, Höppler ball drop

method) 822 cP 393 cP

C) Manufacture of condensation products

Examples 1-7 (a) A portion of the ©% aqueous solution of the polyamidoamide of Experiment © is diluted with a portion of water and now the (g)% solution is heated to (f) ° C. (g) within one hour, the resin is crosslinked at (3) ° C with a portion of a 20% aqueous solution of the crosslinking agent of the test and the pH of the reaction solution is maintained at @ by adding @ part of 50% by weight sodium hydroxide solution. The addition of the crosslinking agent solution takes place in decreasing doses towards the end of resin formation. The amount of crosslinking agent is adjusted to the desired final viscosity; since there is no "Newtonian flow" in the resins, the viscosity was measured at two different shear angular velocities (reported values after three minutes of rotation): shear angular velocity 24.5 s is resin viscosity at the end of crosslinking (n) cP (20 ° C), shear angular velocity 69.5 s 1 cP (20 ° C) (rotational viscometer operating name Haake, Berlin). The pH is (g). The resin solution was neutralized with (r) a portion of 85% formic acid to pH 8 and diluted (§) with a portion of water to give an active ingredient ratio (WS) X of 18%. The viscosity of the final product was Θ at an angular shear rate of 24.5 s ^), respectively © (at an angular shear rate of 69.5 s'1) cP (20 ° C).

For one part of polyamide resin (100%), (7) part of crosslinking agent (100%) was added for crosslinking.

(it) soda liquor, formic acid and water are not counted as WS.

14 61 904

Examples a 400 400 400 400 b 51.6 51.6 50.8 50.8 c '13 13 14 14 d 630 630 620 620 e 20 20 20 20 f 70 65 65 65 g 10.6 10.5 9.8 8.5 h 60-70 60-66 60-68 62-70 f 326 616 508 1016 k 4 5 4 5 1 8.0 0 6.0 0 m 10.6-9.6 10.7-9.2 10.5-9.1 10.5-9.4 n 1525 1220 1400 1218 p 1035 862 1010 873 q 9.8 9.2 9.6 9.4 r 84 79 49 45 s 60 105 113 179 t 1000 764 910,855 u 738,572,652,642 v 0.32 0.60 0.50 1.0 15 61 904 D) Operation

The following tables compare the paper technical properties of the final products with the modified polyethyleneimine (PEI) prepared according to the examples of DT application 1 802 435.

Measurement methods:

Dewatering acceleration:

Described as the reduction in the degree of grinding in ° SR. The degree of grinding in ° SR was determined according to the provisions of leaflet 107 of the Association of Verein der Zellstoff- und Papierchemiker und Ingenieure.

Filler retention:

Describes the association der Verein der Zellstoff. und Papierchemiker und Ingenieure according to leaflet 108 by means of the ash content of paper webs produced with the Rapid-Köthen device.

80% bleached sulphite cellulose of the pulp to be examined

pulp composition: 35% SR

20% kaolin pulp density: 0.24 g / liter

Effect on paper whiteness and effect on optical protein

Described by the whiteness of the ash-free paper webs: pulp composition: 100% bleached sulphite cellulose (35 ° SR) 0.15% optical brightener 0.15% alum 0.06% resin additive

Measurement: remission values%, in a known manner with a Zeiss-Elrepho device, filter R46T with and without UV excitation.

16 61 904

Table 1a:

Dewatering acceleration (measured as reduction in grinding rate in ° SR)

Pulp: newspapers (non-stick ground in Ultraturrax) pH 7.3 pH 5 1.5% alum addition (100% resin, calculated on abs. Dry cellulose) 0.05 0.1% 0.05 0.1% 0- value (without resin addition) (° SR) 61 56 mod. PEI: (DE application publication 1 802 435 according to example 3/4) 59 56 55 53 example 1 57 52 54 51

Table 1b: Filler retention:% ash on paper; addition 0.015% and 0.03% resin (100%) calculated on cellulose and filler fiber suspension pH: 6 4.8 alum addition, calculated on cellulose and filler 0.5% 1.5% 0 value: 9.1 8, 5) mod. PEI: (DE chips- 0.015% increase 10.2 11.1). ,, musjulk. 1,802,435 0.03% increase 11.7 11.8) * according to Example 3 / b) pape Example 1 0.015% increase 10.1 11.0) 0.03% increase 12.0 12.3)

Table 1c:

Effect on Paper Whiteness and Effect on Optical Bleach Zero Value DE Application Public. 1,802,435 Sample according to Example 1, Sample according to Example 3fi with UV 88.7% 78.8% 81.8% without UV 84.2% 76.7% 78.8% 61,904

Table 1a: 17

Dewatering acceleration (measured as reduction in grinding rate in ° SR)

Pulp: newspapers (non-stick ground in an Ultraturrax) pH 7.3 pH 5 1.5 i alum addition (100% resin, calculated on abs. Dry cellulose) 0.05 0.1% 0.05 0.1% 0- value (without resin addition) (° SR) 67 66 mod. PEI: (DE application publication

1,802,435 according to Example 6) 59 56 57 54 Example 2 60 50 57 53

Table 2 b: Filler retention:% ash on paper; addition of 0.015% and 0.03% resin (100%) based on cellulose and filler pH of the fiber suspension: 6 4.8 alum addition, calculated on cellulose and filler 0.5% 1.5% 0 value: 9.3 8, 6%) mod. PEI: (DE chips - 0.015% increase 9.4 11.0) „.

musjulk. 1,802,435 0.03% increase 10.3 11.8) according to Example 6) paper example 2 0.015% increase 11.4 13.0) 0.03% increase 12.1 14.4)

Table 2 c:

Effect on Paper Whiteness and Effect on Optical Bleach Zero Value DE Application Public. 1,802,435 Sample according to Example 2, Sample according to Example 6 with UV 95.8% 79.7% 84.0% without UV 88.9% 77.7% 80.7%

Table 3a: 61904 18

Dewatering acceleration (measured as reduction in grinding rate in ° SR)

Pulp: newspapers (non-stick ground in Ultraturrax) pH 7.3 pH 5 1.5% alum addition (100% resin, calculated on abs. Dry cellulose) 0.05 0.1% 0.05 0.1% o 0 value (without resin addition) (SR) 6.5 62 mod. PEI: (DE application publication

1,802,435 according to Example 1) 59 48 52 49 Example 3 57 47 50 50

Table 3 b: Filler retention:% ash on paper; addition 0.015% and 0.03% resin (100%) calculated on cellulose and filler fiber suspension pH: 6 4.8 alum addition, calculated on cellulose and filler 0.5% 1.5% 0 value: 2.1 2, 4) mod. PEI: (DE chips- 0.015% increase 3.1 5.5)% ash musjulk. 1,802,435 0.03% increase 5.3 6.5) according to Example 1) paper example 3 0.015% increase 4.6 5.6) 0.03% increase 6.5 6.5)

Table 3 c:

Effect on Paper Whiteness and Effect on Optical Bleach Zero Value DE Application Public. 1,802,435 Sample according to Example 3, Sample according to Example 1 with UV 95.8% 82.6% 84.0% without UV 88.9% 78.8% 80.7% 19

Table 4 a; 61904

Dewatering acceleration (measured as reduction in grinding rate in ° SR)

Pulp: newspapers (non-stick ground in Ultraturrax) pH 7.3 pH 5 1.5% alum addition (100% resin, calculated on abs. Dry cellulose) 0.05 0.1% 0.05 0.1% 0- value (without resin addition) (° SR) 66 65 mod. PEI: (DE application publication

1,802,435 according to Example 6) 58 50 56 53 Example 4 57 47 50 50

Table_b £ Filler retention:% ash on paper; addition 0.015% and 0.03% resin (100%) calculated on cellulose and filler fiber suspension pH: 6 4.8 alum addition, calculated on cellulose and filler 0.5% 1.5% 0 value: 2.2 2, 4) mod. PEI: (DE chips- 0.015% increase 4.9 5.0)% ash musjulk. 1,802,435 0.03% increase 7.0 6.3) according to example) paper example 4 0.015% increase 5.3 5.1) 0.03% increase 6.7 5.9)

Table 4 c:

Effect on paper whiteness and effect on optical brightener zero value DE application publication. 1,802,435 Sample according to Example 4, Sample according to Example 6 with UV 88.7% 77.6% 81.8% without UV 84.2% 75.9% 78.8% 61904

Example 5

As shown in B), in Experiment 7, a condensation product is first prepared from adipic acid and diethylenetriamine. According to experiments L3 / (14), this condensation product is grafted onto ethyleneimine in a weight ratio of 1: 1. The obtained reaction product had a viscosity of 400 cP at 20 ° C as a 45% aqueous solution. This condensation product is hereinafter referred to as component a).

The taxon component h) is prepared according to the examples of A) by reacting an ether of dust Ivko 15. having a molecular weight of 1 CHH with epichlorohydrin in a weight ratio of 6.8: 1.

Condensation of components a) and b):

In a reaction vessel equipped with a stirrer, 500 parts of a 23.5% aqueous solution of component a) are weighed and heated to 6 5 ° ('). to a viscosity of 50 cP. As soon as this viscosity is reached, 12 parts of a mixture prepared in advance by combining equal parts by weight of the 23.5% aqueous solution of component a) and 20.5% aqueous solution of component b) described above are added every 10 minutes.

After adding a total of 290 parts of the mixture, the viscosity of the condensation product rises to 200 cP. A mixture containing 6 parts of component a) described above and 3 parts of component b) described above is then added to the reaction mixture again every 10 minutes. After 54 parts of the mixture have been added and the condensation has been continued at 60-65 ° C, the viscosity of the condensation product rises to 900 cP. The reaction product is adjusted to pH 8 with 85% formic acid and finally diluted with water to a solids content of 20%.

This gives a clear aqueous solution of the resin which is practically free of insoluble particles which are too condensed. The resin solution is used in the paper industry as an accelerator for dewatering.

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Example 6

Example F is repeated, with the exception that component a) is a condensation product obtained by reacting the reaction product of adipic acid with Hiethylene triamine and ethanol. in i n birch weight ratio 1 ·?

Also in this case, a resin solution is obtained which is practically free of insoluble particles. The resin solution is used as a flocculant in the paper industry.

Example 7

Components a) and b), described in Example 5, are condensed together as follows: 500 parts of component a) are placed in a pot equipped with a stirrer as a 23.5% aqueous solution and heated to 70 ° C. To this is added 130 parts of component b) as a 20.5% aqueous solution. Both components are first condensed discontinuously to a viscosity of 50 cP. Subsequent quantities of components a) and b) are then added using computer-controlled measuring devices. Before components a) and b) enter the condensing boiler, they are mixed in a small mixer.

The mixture ratio of components a) and b) increases to 1: 1 when the viscosity of the condensation product reaches 120 cP, and the mixture ratio is then continuously reduced to 1: 0.6 when the viscosity of the condensation product reaches 250 cP and to 1: 0.3 when the viscosity reaches 700 cP. A total of 250 parts of component a) and 200 parts of component b) are required, based on the solid product in each case. The condensation product is finally adjusted to pH 8 with 85% formic acid and diluted with water to a solids content of 20%. The condensation product is used as a retention aid in the paper industry. The condensation product does not contain insoluble particles.

22 61 90 4

Example 8 1752 g of adipic acid and 1360 g of diethylenetriamine (molar ratio 1: 1.1) are condensed by heating for 8 hours at 150-170 ° C. It is then diluted with 2890 g of water to give a solution containing 47.1% by weight of solids. The viscosity of a 45% aqueous solution is 140 mPas.

To 1200 g of the product obtained are added 12 g of concentrated sulfuric acid and then 1800 g of a 50% aqueous solution of ethyleneimine. A grafted polyamidoamine is obtained which contains 6.7 ethyleneimine units per basic nitrogen group and has a viscosity of 453 mPas.

A 50% aqueous solution of the resulting ethyleneimine-grafted polyamidoamine (50 g) was diluted with 542 g of water and then reacted in a weight ratio of 1: 0.3 at 75 ° C at pH 9-10 for 2 hours with polyalkylene oxide dichlorohydrin ether ( 75 g) (crosslinking agent VI) containing 9 ethylene oxide units. During the reaction, water is continuously added to the reaction mixture in such an amount as to obtain a 20% aqueous solution of the condensation product; its viscosity is 584 mPas. There is 0.07 gaps of crosslinking agent VI in the grafted polyamidoamine per gap of the nitrogen-containing group.

Table 5 shows the effect of the obtained condensation product on the dewatering acceleration. The resin solutions prepared in Reference Examples a) to e) have been used as reference substances.

Comparative Example a) (Product of DE 1 771 814) 1460 g of adipic acid were condensed at 150-175 ° C with diethylene triamine (1030 g) and caprolactam (565 g) (molar ratio 1: 1: Q, 5) for 7 hours. I drive. Water was added to the reaction mixture to give a solids content of 2695 g to 46.9% by weight. The viscosity of the 45% aqueous solution at 20 ° C was 662 mPas.

An aqueous solution of 800 g of the condensation product obtained above containing 22% solids was crosslinked with epichlorohydrin (5.07 g) at pH 9-10 at 70-75 ° C for 4 hours. The viscosity of the 20% aqueous solution was 800 mPas. 0.058 moles of epichlorohydrin was used per gap of the nitrogen-containing group of polyamidoamine.

23 619 0 4

Comparative Example b) (Product according to DE 1 771 814) 900 g of a 22% solution of the condensation product prepared from adipic acid, diethylenetriamine and caprolactam in Comparative Example a) were reacted at pH 9-10 at 70-75 ° C for 4 hours. polyethylene glycol dichlorohydrin ether (9 ethylene oxide units) (29.7 g) (crosslinking agent VI). 0.09 g of crosslinking agent VI was used per one basic nitrogen group of the polyamidoamine. The viscosity of a 20% aqueous solution of the condensation product at 20 ° C was 400 mPas.

Comparative Example c) (DE-A-1 795 392) 1752 g of adipic acid were condensed at 15 ° C to 170 ° C for 8 hours with diethylenetriamine (1360 g) (molar ratio 1: 1.1), and the resulting reaction mixture was diluted to a solids content of 47.1% by weight. % by adding 2890 g of water. The viscosity of the 45% solution was 140 mPas. 600 g of a 22% aqueous solution of the obtained condensation product was reacted with the crosslinking agent shown in Example 2.1 of the DE application (80.5 g) at 70 ° C at pH 9-10. The viscosity of a 20% solution of the obtained product at 20 ° C was 45 ° mPas.

Comparative Example d) Pages 15 and 16 of DE 2 156 215) Polyamine 4 was prepared exactly according to the instructions. However, the viscosity of a 20% aqueous solution of the obtained product at 20 ° C was 230 mPas. The effect of this condensation product as a dewatering aid is shown in Table 5.

Comparative Example e) (Product of DE-A-2 156 215) In page 14 (a) of DE-A-polyamine 4, a condensation product modified with sodium chloroacetate (600 g) was reacted in a 22% aqueous solution at 75 ° C with crosslinking agent VI (polyethylene). with 9 ethylene oxide units) with an 18% aqueous solution (133.1 g). A 2% aqueous solution of the obtained product had a viscosity of 1500 mPas. 0.092 crosslinking agent was used per basic nitrogen group of polyamidoamine.

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Table 5

Dewatering (measured as reduction in degree of grinding in ° SR) at pH 7.9.

Newspapers ground without sticks in an Ultra-Turrax were used as the test mass. The zero value (without resin addition) was 71.

Condensation product Resin added (% by weight) ° SR

The resin prepared in Example 8 0.04 · 55 η’πο ^ Q, 08 40 0.10 36

Comparative Example a) 0.05 51 0.10 44 b) 0.08 48 c) 0.04 59 0.08 51 d) 0.05 55 0.10 52 e) 0.05 55 0.10 51 .1 "

Claims (2)

61904 25 A process for the preparation of nitrogen-containing condensation products by the reaction of polyamidoamines with a crosslinking agent, which polyamidoamines are prepared from 1 mole part of C 1 -C 6 g-dicarboxylic acid and 0.8 to 1.4 mole parts of 3 to 10 basic nitrogen atoms per molecule 10% by weight of diamine, and in which 2 to 8 ethyleneimine units per basic nitrogen group have been added, characterized in that one part by weight of said polyamidoamine is reacted at 20 to 100 ° C. 3 to 2 parts by weight of a polyalkylene oxide containing 8 to 100 alkylene oxide units, the terminal OH groups of which have been reacted with at least an equivalent amount of epichlorohydrin, allowing the reaction to continue until a high molecular weight, still water-soluble resin having a viscosity of 20 At 20 ° C, a 20% aqueous solution has more than 300 mPa.s. Process according to Claim 1, characterized in that a discontinuous part of the polyamidoamine and the polyalkylene oxide derivative is first condensed, after which a mixture of polyamidoamine and the polyalkylene oxide derivative is added continuously or in batches to the condensation product.