DE19600366A1 - Narrowing molecular weight distribution of ethyleneimine polymer] - Google Patents

Abstract

Molecular weight distribution of an ethyleneimine polymer is narrowed by subjecting a solution of the polymer to ultrafiltration, removing 5-95 wt.% of the polymer as permeate, and optionally isolating the remaining polymer from the retentate.

Description

The invention relates to a method for producing water soluble polymers containing ethyleneimine units with a narrow molecular weight distribution through ultrafiltration and use of the retentate available from ultrafiltration as Retention, drainage and fixative in the manufacture of paper, as a promoter in the sizing of paper with alkyldi ketenen, as a flocculant for sewage sludge, as an adhesion promoter in the production of composite films, as an additive in hair and Skin care products and as a means of immobilizing anioni active substances.

Polymers containing ethyleneimine units, especially poly ethyleneimine, have long been used as a retention, drainage and fixatives used in the manufacture of paper. The known polymers containing ethyleneimine units have a broad molecular weight distribution. For example, polyethyleneimine by polymerizing ethyleneimine in the presence of acids, Le wis acids or halogen alkanes prepared, cf. for example US-A-2 182 306 and US-A-3 203 910.

From US-A-4 066 494 is the use of nitrogenous Condensation products based on polyalkylene polyamines as Drainage accelerator and retention aid in the paper industry known. The nitrogenous condensation products are by reacting polyalkylene polyamines, the 15 to Contain 500 alkyleneimine units, with α, ω-chlorohydrin ethers of polyethylene oxides containing 18 to 90 ethylene oxide units included, at 20 to 100 ° C with formation of high molecular weight, still water-soluble resins.

DE-C-29 16 356 describes a process for the production of known water-soluble polyether amines, in which one or Polyamines with 2 to 10 nitrogen atoms with chlorohydrin ethers 1 mole of a dihydric alcohol with 2 to 5 carbon atoms, their ethoxylation products containing up to 18 ethylene oxide units ten contain glycerin or polyglycerin containing up to 15 glyce contains pure units, and at least 2 to 8 moles of epichlorohydrin first in polar, water-miscible solvents in Ab presence of water or with the substantial exclusion of water condensed at temperatures from 110 to 200 ° C and then a Alkali metal or alkaline earth metal base in such an amount  admits by at least 20% of the condensation To neutralize hydrogen chloride. This is followed by another post-condensation. The condensation products are called Flocculants, retention aids and drainage agents from the manufacturer position of paper used.

WO-A-94/12560 contains further ethyleneimine units tend polymers known, which are obtainable in that Polyalkylene polyamines, preferably polyethyleneimine, by reaction initially with, for example, monocarboxylic acids amidated and the resulting reaction products to be crosslinked with at least bifunctional crosslinkers Polyalkylenpolyaminen react, which in 20 wt .-% aq ger solution at 20 ° C have a viscosity of at least 100 mPa · s. These polymers are also used as drainage, flocculation and retention aids as well as fixatives in the manufacture used by paper.

WO-A-94/14873 likewise discloses water-soluble ethyleneimine Unit-containing polymers known, which are thereby obtainable are that Michael addition products of, for example, poly alkylene polyamines, polyamidoamines or grafted with ethyleneimine polyamidoamines and monoethylenically unsaturated carbon acids, salts, esters, amides or nitriles of monoethylenic unsaturated carboxylic acids, with at least bifunctional Crosslinkers react to water-soluble condensation products lets in a 20 wt .-% aqueous solution at 20 ° C a viscose of at least 100 mPa · s. The polymers are called Ent watering, flocculating and retention agents in the manufacture used by paper.

The water-soluble polymers containing ethyleneimine units described above usually have a very wide molar mass distribution M _w / M _n .

The present invention has for its object a Ver drive to the production of water-soluble, ethyleneimine units containing polymers with a narrower molecular weight distribution for To make available.

The object is achieved with a method for Production of water-soluble ethyleneimine units ent holding polymers with a narrower molar mass distribution if one from Solutions of polymers containing ethyleneimine units with the usual broad molecular weight distribution by ultrafiltration Membranes 5 to 95 wt .-% of polymers, based on the set polymers, separates as permeate and the ethyleneimine  units containing polymers with a narrower molecular weight distribution isolated from the retentate if necessary.

These polymers can be obtained by using water-soluble, Polymers with broad molecular weights containing ethyleneimine units Distribution of ultrafiltration on membranes with a separation limit for polymers with molecular weights of at least 1000, where 30 to 70% by weight, based on the polymers used separates out low molecular weight components as permeate and the high mole kular parts optionally isolated from the retentate. The off Separate low molecular weight proportions of polymers are preferred wise for the synthesis of widely distributed, water-soluble ethylene Polymers containing imine units, which are then used again be subjected to ultrafiltration on membranes, 5 up to 95% by weight, based on the polymers used separates molecular polymers as permeate.

The high molecular weight fraction remaining in the retentate is narrower distributed water-soluble containing ethyleneimine units Surprisingly, polymers have been used compared to those previously used polymers with a broad molecular weight distribution have a clear ge increased effectiveness as drainage, retention and floc agent in the manufacture of paper.

The water-soluble polymers according to the invention containing ethyleneimine units and having a narrower molar mass distribution M _w / M _n of up to 350, preferably 2 to 300, are produced by ultrafiltration of polymers containing ethyleneimine units and having a broad molar mass distribution. For example, crosslinked polyamidoamines grafted with ethyleneimine have a molecular weight distribution M _w / M _n of 400. The molecular weight distribution is determined by gel permeation chromatography on a Pullulan standard with water as the eluent. The retentates produced according to the invention have, for example, viscosities of 120 to 3000, preferably 200 to 1500 mPa · s (measured in a Brookfield viscometer of 10% by weight polymer solutions at 20 ° C. and pH 10) and a molar mass distribution M _w / M _n from 2 to 350, for example, preferably 10 to 300.

For the ultrafiltration you can use all commercially available Use membranes that have a cut-off limit for Polymers with molecular weights of e.g. B. 200 to 1 million, preferably of at least 1000. Mem is particularly preferably used branches with separation limits for molecular weights from 3000 to 500000, ins special membranes with separation limits for molecular weights of 100,000. The separation limit of the membranes used is the mole adjust the weight distribution of the polymers so that the  Separation of 5 to 95 wt .-% of polymer is possible. In the Ultrafiltration then becomes the low molecular weight portion of the Po lymeren, whose molar mass is below the separation limit, as Per meat separated. The higher molecular weight An remains in the retentate parts of polymer. By separating the low molecular weight An Parts are obtained with polymers containing ethyleneimine units narrower molecular weight distribution.

The membranes can be, for example, in the form of tubes, hollow fibers, plate devices or spiral winding modules the. Suitable materials for the membranes are, for example regenerated cellulose, cellulose acetate, cellulose triacetate, Po lyamide, polyacrylonitrile, acrylonitrile copolymers, polysulfone, Copolymers of vinyl chloride, polyimide, polyvinylidene fluoride, Polytetrafluoroethylene, polymethyl methacrylate, hydrolyzed Copolymers of ethylene and vinyl acetate, with hydrolysis degree of vinyl acetate groups of at least 50%, polycarbonate, Polypropylene or mineral or ceramic membranes. Before membranes based on polysulfone are preferably used. About ultrafiltration and suitable membranes for example, summarized by Munir Cheryan in Ultrafiltration Handbook, Technomic Publishing Company, Inc., 1986.

Membranes that are suitable for ultrafiltration are manufactured by offered to numerous companies, cf. International Meeting Catalog for chemical engineering and biotechnology ACHEMA 94, Frankfurt on the Main river.

Ultrafiltration of the aqueous solutions of ethyleneimine units ten containing polymers with a broad molecular weight distribution performed in the usual way. It is preferable to work at Room temperature and sets aqueous solutions of ethyleneimine unit containing polymers. The temperature of the aqueous Polymer solutions can e.g. B. are in the range of 10 to 80 ° C. The ultrafiltration can be under atmospheric pressure or under increased pressure on the retentate side e.g. B. at pressures of 1.5 to 50, preferably 2 to 20 bar. Of the pH of the aqueous solutions of ethyleneimine units ent holding polymers in ultrafiltration z. B. 2 to 14, preferably 8 to 12.

The ultrafiltration of the water-soluble, ethyleneimine units containing polymers with a broad molecular weight distribution is in carried out in such a way that 5 to 95, preferably 20 to 90% by weight, based on the polymers used, of polymers  separates as permeate and the polymers with a narrower molar mass division if necessary isolated from the retentate.

According to the method of the invention, all of them can be dissolved in water Lichen, polymers containing ethyleneimine units in narrower distributed polymers with high molecular weight and in polymers be separated with low molecular weight fractions. Ethyleneimine On polymers containing units are known. It comes to this both homopolymers and polymers into consideration for example, contain grafted ethyleneimine. The homopoly Merisate are for example by polymerizing ethylene imine in aqueous solution in the presence of acids, Lewis acids or alkylating agents such as methyl chloride, ethyl chloride, Pro pyl chloride, ethylene chloride, chloroform or tetrachlorethylene produced. The polyethyleneimines available in this way have one Wide molecular weight distribution and molecular weights of 129, for example to 2 x 106, preferably 430 to 1 x 106.

Another group of poly containing ethyleneimine units mers are polyamidoamines grafted with ethyleneimine which are used in the to the prior art US-A-4 144 123 described the. The polyamidoamines are, for example, by reacting Dicarboxylic acids with 4 to 10 carbon atoms with polyalkylene polyamines, which preferably have 3 to 10 basic nitrogen atoms in the Contain molecule, made. Suitable dicarboxylic acids are for example succinic acid, maleic acid, adipic acid, glutar acid, suberic acid, sebacic acid or terephthalic acid. One can also use mixtures of different dicarboxylic acids, e.g. B. Mixtures of adipic acid and glutaric acid or maleic acid and Adipic acid. Adipic acid is preferably used for the preparation the polyamidoamines. Suitable polyalkylene polyamines, which with the Dicarboxylic acids are condensed, for example, diethylene triamine, triethylene tetramine, dipropylenetriamine, tripropylene tetra min, diheptamethylenetriamine, aminopropylethylenediamine and bis- Aminopropyl ethylenediamine. The polyalkylene polyamines can also be used in Form of mixtures used in the manufacture of polyamidoamines be set. The polyamidoamines are preferably by Condensation of dicarboxylic acids and polyamines in substance poses. However, the condensation can optionally also be carried out in an inert manner th solvents. The condensation of the Dicarboxylic acids with the polyalkylene polyamines are usually used in the temperature range from 120 to 220 ° C, for example leads, whereby the water formed during the reaction from the Distilled reaction mixture. The condensation can exist if additionally in the presence of lactones or lactams of Carboxylic acids with 4 to 8 carbon atoms are made, e.g. B. in the presence of caprolactam. Per mole of a dicarboxylic acid  for example, 0.8 to 1.4 moles of a polyalkylene po are used lyamins. The polyamidoamines thus obtainable have primary and secondary NH groups, optionally also tertiary nitrogen atoms and are soluble in water.

The polyamidoamines described above are ge with ethyleneimine by, for example, ethyleneimine in the presence of Acids (e.g. sulfuric acid or phosphoric acid) or in the presence from Lewis acids (e.g. boron trifluoride etherates) to the polyamido can act on amines. For example, one can be more basic Nitrogen grouping in polyamidoamine 1 to 50, preferably 2 grafting up to 25 ethyleneimine units, d. H. to 100 weight Parts of a polyamidoamine are used, for example, about 10 to 500 parts by weight of ethyleneimine.

Polymers containing ethyleneimine units also come Reaction products into consideration by grafting polyamido amines with ethyleneimine and subsequent reaction with at least two functional groups containing crosslinkers can be prepared are. Products of this type are, for example, according to the teaching the above-mentioned US-A-4 144 123 as retention, flocculation and Dewatering agents used in the manufacture of paper.

Except for the bishlorohydrin described in US-A 4 144 123 ethers of polyalkylene glycols as at least two functional Crosslinkers containing groups are suitable for α, ω-dichloropolyalky lenglycols, for example as crosslinkers from EP-B-0 025 515 are known. They are available by two to tetravalent alcohols, preferably alkoxylated two to four quality alcohols either

• 1. with thionyl chloride with elimination of HCl and subsequent ka analytical decomposition of the chlorosulfonated compounds un ter sulfur dioxide elimination or
• 2. with phosgene with HCl elimination in the corresponding bis chlorocarbonic acid esters and then by catalytic decomposition with carbon dioxide elimination α, ω-dichloro ether is obtained.

The alcohol component used is preferably ethoxylated and / or propoxylated glycols used with 1 to 100, in particular 4 to 40 moles of ethylene oxide per mole of glycol reacted will.  

Other suitable crosslinkers are α, ω- or vicinal dichloroalkanes, for example 1,2-dichloroethane, 1,2-dichloropropane, 1, 3-dichloro propane, 1,4-dichlorobutane and 1,6-dichlorohexane. Examples of white Other crosslinkers are the reaction products of at least three valuable alcohols with epichlorohydrin to reaction products that have at least two chlorohydrin units, e.g. B. used one as polyhydric alcohols glycerin, ethoxylated or propoxy gated glycerols, polyglycerols with 2 to 15 glycerol units in the molecule and optionally ethoxylated and / or propoxy gated polyglycerols. Crosslinkers of this type are, for example known from DE-A-2 16 356. Crosslinkers are also suitable which contain blocked isocyanate groups, e.g. B. Trimethylhexame ethylene diisocyanate blocked with 2,2,3,6-tetramethylpiperidinone-4.

Such crosslinkers are known, cf. for example DE-A-40 28 285, and crosslinkers containing aziridine units based on polyethers or substituted hydrocarbons, e.g. B. 1,6-bis-N-aziridinohexane, cf. US-A-3 977 923. It is of course also possible, mixtures of two or more Ren crosslinkers to use to increase molecular weight.

The crosslinkers described above can be used either alone or in Mixture in the reaction with ethyleneimine units containing Polymers are used. The crosslinking reaction will in all cases at most so far that the resulting Products are still water-soluble, e.g. B. should be at least 10 g of the crosslinked polymer in 1 liter of water at a temperature of Loosen 20 ° C. The crosslinking reaction takes place in a known manner by heating the reaction components at temperatures of 50 to 220, preferably at temperatures of 60 to 100 ° C. Provided the crosslinking reaction at temperatures above 100 ° C in aqueous medium is carried out, you need pressure-tight designed apparatus, e.g. B. equipped with a stirrer autoclaves.

Polymers containing ethyleneimine units also come Reaction products into consideration, which are obtainable by implementation from Michael addition products

• - Polyalkylene polyamines, polyamidoamines, with ethyleneimine grafted polyamidoamines and mixtures of the above Connections and
• monoethylenically unsaturated carboxylic acids, salts, esters, Amides or nitriles of monomethylenically unsaturated Carboxylic acids, chlorocarboxylic acids, glycidylic acid, alkali salts the glycidyl acid or / or glycidyl acid amide

With
at least bifunctional crosslinkers. Such reaction products are known for example from WO-A-94/184743. In addition to the halogen-containing crosslinking agents, the classes of halogen-free crosslinking agents described above are particularly suitable for their manufacture.

Another class of poly containing ethyleneimine units meren is known from WO-A-94/12560. It is about this to cross-linked, partially amidated polyethyleneimines that get are through

• - Reaction of polyethyleneimines with
• monobasic carboxylic acids or their esters, anhydrides, Acid chlorides or acid amides and
• - Implementation of the amidated polyethyleneimines with at least two Crosslinkers containing functional double bonds.

The molecular weights of the polyethyleneimines in question can amount to up to 2 million and are preferably in the range of 1000 to 50000. The polyethyleneimines are partially based carboxylic acids amidated so that, for example, 0.1 to 90, preferably 1 to 50% of the amidatable nitrogen atoms in the Polyethyleneimines is present as an amide group. Suitable, at least two crosslinkers containing functional double bonds are above called. Halogen-free crosslinkers are preferably used.

In the reaction of polymers containing ethyleneimine units with crosslinkers, for example, 1 part by weight of one Compound containing ethyleneimine units 0.001 to 10 preferably 0.01 to 3 parts by weight of at least one crosslinker a.

Polymers containing ethyleneimine units can also quaternized polyethyleneimines can be used. The quaterni Sation of the polyethyleneimines can, for example, with alkyl halogens niden such as methyl chloride, ethyl chloride, hexyl chloride, benzyl chloride or lauryl chloride and with, for example, dimethyl sulfate can be made. Other suitable ethyleneimine units Polymers containing th are modified by Strecker reaction graced polyethyleneimines, e.g. B. the reaction products of poly ethyleneimines with formaldehyde and hydrogen cyanide and hydrolysis the resulting nitriles. Phosphono are also suitable methylated polyethyleneimines and alkoxylated polyethyleneimines,  which, for example, by reacting with polyethyleneimine Ethylene oxide and / or propylene oxide are available. Such alkoxy gelled polyethyleneimine contain 1 to 100 per NH group preferably 2 to 20 alkylene oxide units. The molecular weight of the poly ethyleneimine can be up to 2 million. Preferably polyethyleneimines with molecular weight are used for the alkoxylation from 1000 to 50000.

Other suitable polymers containing ethyleneimine units are Reaction products of polyethyleneimines with diketenes, e.g. B. from Polyethyleneimines with a molecular weight of 1,000 to 50,000 with stearyl diketen. The ethyleneimine units described above ent holding polymers with a broad molecular weight distribution subject to ultrafiltration according to the invention. The here as Permeate separated low molecular weight fraction of polymers who for the synthesis of widely distributed, water-soluble ethylene Polymers containing min units used, which then again be subjected to ultrafiltration on membranes, 5 up to 95% by weight, based on the polymers used separates molecular polymers as permeate. The low molecular weight Shares can thus be obtained from the water-soluble ethyleneimine unit abge containing polymers with a broad molecular weight distribution separates and after increasing the molecular weight in the process of Ultrafiltration can be recycled. Unless the concentration the separated low molecular weight fraction of polymers in the Per meat is too low, the permeate is distilled off Concentrated water, e.g. B. make a concentration of 5 to 50, preferably 10 to 30 wt .-% of polymer. The one in the separated permeate contained low molecular weight components Polymers can be reacted with ethyleneimine, for example.

The reaction is carried out in an aqueous medium, for example at tempera tures from 50 to 200 ° C under the influence of acids such as sulfur acid or phosphoric acid or by Lewis acids.

The ones separated off in the ultrafiltration with the permeate Molecular proportions of polyme containing ethyleneimine units Ren can also have at least two functional groups send crosslinkers to higher molecular weight polymers with a wide mol mass distribution to be implemented. Suitable crosslinkers are already been given above.

The low molecular weight An separated in the ultrafiltration Parts of polymers can also be used to make products with porridge ter molecular weight distribution be worked up that one too next reacted with ethyleneimine and the reactants obtainable in the process on products with at least two functional groups Crosslinkers can react. These polymers obtainable with  broad molecular weight distribution are returned to ultrafiltration led to the high molecular weight components with narrower mol mass distribution and a viscosity of at least 120 mPa · s (measured in 10 wt .-% aqueous solution at 20 ° C and pH 10) win. The higher molecular or high molecular weight proportions of Po containing ethyleneimine units Lyers can optionally be isolated from the aqueous solutions by evaporating the water. The vast majority of the Polymers containing narrower moles containing ethyleneimine units however, mass distribution is used in the form of aqueous solutions det. The concentration of the aqueous solutions is, for example wise in the case of those grafted and crosslinked with ethyleneimine Polyamidoamines 5 to 25, preferably 7 to 15 wt .-%.

Those containing ethyleneimine units are particularly preferred Polymer crosslinked polyamidoamines grafted with ethyleneimine Base of adipic acid and diethylene triamine and / or triethylene tetramine used. Such condensation products are for example as from the prior art US-A-4 144 123 be knows. Among the particularly preferred cross-linked with ethyleneimine grafted polyamidoamines include those reaction products which are available in the presence of halogen-free crosslinkers.

The Michael addition products from Polyether diamines with molecular weights from 400 to 5000 or of poly amines with molecular weights from 129 to 50,000 of acrylic acid ester or the reaction products of maleic anhydride with polyether dia mines of formula (I) given above are particularly preferred.

The water-soluble polymers containing ethyleneimine units with a molar mass distribution M _w / M _n of 2 to 350 with a viscosity in 10% strength aqueous solution at 20 ° C. and pH 10 of at least 120 mPa · s are obtained as retentate in the ultrafiltration .

These more narrowly distributed polymers containing ethyleneimine units Ren are used as retention, drainage and fixative used in the manufacture of paper. You will for this purpose the paper stock in the usual amounts of, for example, 0.01 up to 1 wt .-% added. Compared to the same amount of wide distributed polymers containing ethyleneimine units of the same Composition you get a surprisingly increased reten effect and drainage. The ultrafiltration as Proportions of retentate polymer are also considered Flocculant for sewage sludge, as an adhesion promoter at Her Provision of composite films, as an additive in hair and skin care means and as a means of immobilizing anionic activity fabrics z. B. used in the manufacture of medicines.  

The percentages in the examples mean percent by weight.

The viscosities were determined in a Brookfield viscometer at 20 ° C. a concentration of 10 wt .-% and a pH of 10 measured unless otherwise indicated in the examples.

Examples Polymer 1

According to the regulation given in US-A-4 144 123, Ex. 3 is by condensing adipic acid with diethylenetriamine Made polyamidoamine and then with so much ethyleneimine grafted that the polyamidoamine per basic nitrogen grouping contains 6.7 grafted ethyleneimine units.

The polyamidoamine grafted with ethyleneimine is then crosslinked by reaction with a bis-glycidyl ether of a polyethylene glycol having an average molecular weight of 2000. A polymer containing ethyleneimine units is obtained with a broad molar mass distribution (M _w / M _n of 400) and a viscosity of 120 mPa · s (determined in a 10% strength aqueous solution at 20 ° C. and pH 10). The concentration of the aqueous solution is 12.5%.

Polymer 2

Copolymer of acrylamide and dimethylaminoethyl acrylate, the is quaternized with methyl chloride containing acrylamide of 84 mol% and a molar mass of approx. 10 million

example 1

4.8 kg of the 12.5% aqueous solution of Po described above lymer 1 were subjected to ultrafiltration on a membrane with a Separation limit for polymers with molecular weights of 100,000.

The membranes were in the form of a hollow fiber cartridge (manufacturer A / G-Technology (USA)). The volume on the retentate side was maintained by adding 10 kg of water. The ultrafiltration was stopped after the conductivity of the permeate was below 200 μS / cm. On the retentate side, after completion of the ultrafiltration, there was 40% of a water-soluble polymer 1 containing ethyleneimine units with a molar mass distribution M _w / M _n of 15. The viscosity of the more narrowly distributed polymer was 520 mPa · s (measured in 10% strength aqueous solution) Solution at pH 10 and 20 ° C). 60%, based on polymer 1, were separated off as meat. The permeate was concentrated using a falling film evaporator to a concentration of 45%. The viscosity of the separated low molecular weight fraction was 24 mPa · s (determined in 10% aqueous solution at 20 ° C and pH 10).

Example 2

Example 1 was repeated with the exception that 2 kg of water were added while maintaining the volume on the retentate side. After completion of the ultrafiltration, there was 60% on the retentate side, based on polymer 1. This polymer had a molar mass distribution M _w / M _n of 300 and a viscosity of 150 mPa · s (measured in 10% strength aqueous solution at 20 ° C.) . The polymer concentration of the permeate was adjusted to 45% by distilling off water on a falling film evaporator. The low molecular weight polymer components of the permeate had a viscosity of 25 mPa · s.

Example 3

In a flask with a stirrer and a reflux condenser was equipped, 100 g of that in Example 1 were separated low molecular weight polymers in the form of the 45% aqueous solution treated with 1.7 g of 96% sulfuric acid and brought to a temperature heated from 85 ° C. As soon as this temperature was reached, they were given 50 g of ethylene imine as a 60% aqueous solution. In the course of A reaction lasting 6 h was added to 66 g of water.

Example 4

In a flask equipped with a stirrer and reflux condenser 100 g of the low molecular weight separated according to Example 1 Portions presented as a 45% aqueous solution, with 1.7 g of 96% Added sulfuric acid and heated to a temperature of 90 ° C.

As soon as this temperature was reached, 100 g of ethylene imine were added as a 60% aqueous solution and added in the course of the reaction another 107 g of water.

Example 5

50 g of low molecular weight polymer, which is used as the permeate in Example 1 was obtained as a 25% aqueous solution in a flask submitted, which was equipped with stirrer and reflux condenser.

At a temperature of 70 ° C, 13.5 g of a 20% strength was added aqueous solution of the bis-glycidyl ether of a polyethylene glycol to the molecular weight 2000. Then the pH of the reacti Mixture set to 7.8. The reaction solution contained 26.6% solids and had a viscosity of 625 mPa · s.  

Example 6

50 g of the reaction product from Example 3 were as 25% submitted aqueous solution in a reactor, heated to 70 ° C and by adding 12 g of a bis-glycidyl ether of polyethylene glycol with a molecular weight of 2000 in the form of a 20% crosslinked aqueous solution. The pH of the reaction product was set to 7.8. The aqueous solution had a solid content of 26% and a viscosity of 670 mPa · s.

Example 7

50 g of the reaction product described in Example 4 were in Form presented a 25% aqueous solution in a reactor and at a temperature of 70 ° C with 10 g of the bis-glycidyl ether a polyethylene glycol of molecular weight 2000 in the form of a 20% crosslinked aqueous solution. The pH was measured after the Response set to 7.8. An aqueous solution was also obtained a solids content of 27.1% and a viscosity of 610 mPa · s (determined at 20 ° C).

The products described above were used as drainage, reten tion and fixative tested in the manufacture of paper. The drainage time was used as a measure of the drainage performance determined according to Schopper-Riegler. As a measure of the retention of Fiber, fine and fillers became the optical permeability of the running white water. The measurements were made with the help of a photometer from Lange at 340 nm.

As a measure of the fixing performance of fine and fillers (Reini closed closed water circuits) the absorbance (Lange photometer, 588 nm) in with fixative acted water measured. As a comparison with the state of the art Polymer 1 was not used.

The measurement results given below are mean values from 5 Measurements. Retention and drainage agents were in quantities from 0.1 to 0.4 and fixative in amounts from 0.5 to 2% by weight, each based on the solids, added to the paper stock.  

Example 8

From 100 parts of unprinted newsprint with a filler holds 10% and 40 parts of natural chalk (type DX 1 der Omya) was a pulp with a consistency of 5 g / l and a degree of grinding of 50 ° SR (Schopper-Riegler). The pH Pulp value was 7.7. The paper stock was used in several pro ben divided, which then with the amounts given in Table 1 Polymers were added. The drainage from each sample was times for 600 ml of filtrate in the Schopper-Riegler test device determined.

In a modification of the above-mentioned regulation, Comparative Example 1 the drainage rate for the Paper stock specified above in the absence of a polymer Right. The results are shown in Table 1.

Table 1

Example 9

The paper stock described in Example 8 was with the exception of Comparative Example 4 with the amounts given in Table 2 Polymer added and each with a test paper machine a fourdrinier sieve and connected Akumat (upper sieve) in one Machine speed of 50 m / min and a web width of 74 cm processed into paper with a basis weight of 80 g / m².

With the help of an automatic measuring system, the The filler content of the paper is determined automatically. Of the The filler content of the paper is shown in Table 2 in each case.

It is a measure of filler retention.

Table 2

Example 10

A pulp was made from 100 parts of printed newsprint a consistency of 5 g / l and a freeness of 50 ° SR poses. The pH of the pulp was 7.7. To sample this With the exception of Comparative Example 7, the pulp used in Table 3 each indicated amounts of polymers added and the drainage times for in a Schopper-Riegler test device 600 ml of filtrate measured in each case. The results obtained are given in Table 3.

Table 3

Example 11

The paper stock described in Example 10 was in each case with the Amounts of polymers given in Table 4 and added a test paper machine with a fourdrinier and connected Akemat and a web width of 74 cm with a machine narrow speed of 55 m / min to paper with a basis weight of 70 g / m² drained. With the help of an automatically working measurement the filler content in the paper was determined, which is a measure for filler retention. The results obtained are given in Table 4. In Comparative Example 10 ent described in Example 10 ent without further addition watered.

Table 4

Example 12

Made from 50 parts bleached pine sulfate pulp, 50 parts ge bleached beech sulfite pulp and 30 parts of a natural Chalk (type DX 1 from Omya) became a pulp with a Fabric density of 5 g / l and a freeness of 27 ° SR.

The pH of the pulp was 7.2. Except for comparison Example 13 became samples of this paper stock in Table 5 specified amounts of polymer are added and in each case the dewatering times for 600 ml of filtrate in a Schopper-Riegler test machine definitely advises. The drainage times are given in Table 5 ben.

Table 5

Example 13

From the paper stock described in Example 12 with Aus from Comparative Example 16, the menu shown in Table 6 gene added to polymer. On a test paper machine with a fourdrinier sieve and connected Akumat (upper sieve) and one Web width of 74 cm were used with different machine sizes Velocity paper with a basis weight of 70 g / m² poses. The filler content of the papers was determined using an au automatic measuring system. The test conditions and results are given in Table 6.

Table 6

Example 14

From 100 parts of unprinted newsprint with a filler holds about 10% and 10 parts of China Clay (Type X 1 from the company ECC) becomes a pulp with a consistency of 5 g / l and a Grinding degree of 50 ° SR produced. The pH was 7.6. With off Taken from comparative example 19 were each for this paper stock Weil added the amounts of polymer given in Table 7 and the drainage times of the pulps thus obtained in a Schopper-Riegler test device and the optical transmission of the white water. The results are shown in Table 7 give.

Table 7

Examples 15 to 17

From 100 parts of unprinted newsprint with a filler holds 10% and 10 parts of China Clay from ECC, Type X 1, becomes a pulp with a consistency of 2.2 g / l and a grinding degree of 50 ° SR. The pH of the pulp was 7. Mit Except for Comparative Example 21, samples of this paper are used in each case the polymer specified in Table 8 in the added amount specified there. After being mixed the samples were each dewatered in a Schopper-Riegler test device and the drainage time for 1000 ml of filtrate was determined. In Ta belle 8 is also the optical permeability of the filtrate specified.

Table 8

Examples 18 to 20

From 100 parts of unprinted newsprint with a filler holds about 10% and 10 parts of China Clay from ECC, Type X 1, as well as 0.5% alum, based on dry matter a pulp with a consistency of 2.2 g / l and a freeness manufactured from 50 ° SR. The pH of the pulp was 6.0. With off Comparative Example 23 was taken as samples of this paper substance the amounts of Polymerisa given in Table 9 added and the drainage time for 1000 ml of filtrate in a Schopper-Riegler test device. In addition, in Ta belle 9 indicated the optical permeability of the filtrate.

Table 9

Examples 21 to 23

Made from 33 parts of unprinted newsprint, 33 parts of corrugated cardboard and 33 parts of printed LWC paper becomes a pulp with a Fabric density of 2 g / l and a freeness of 50 ° SR.

The pulp pH was 7. Except for comparison Example 25 was made into samples of this paper stock in Ta belle 10 each stated amounts of polymers added and the drainage times for 1000 ml of filtrate in a Riegler test device determined. In addition, the optical transmission liquid of the filtrate measured. The results are in Table 10 specified.  

Table 10

Examples 24 to 26

Made from 33 parts of unprinted newsprint, 33 parts of corrugated cardboard and 33 parts of printed LWC paper becomes a pulp with a Fabric density of 2 g / l and a freeness of 50 ° SR.

The pH of the pulp was 7. This pulp was put at 0.2% Water glass (solid), based on dry paper stock too. With off Comparative Example 27 was taken as a sample of this Pulp each the amounts of Po given in Table 11 lymer and determined the drainage times for these samples in a Schopper-Riegler test device for 1000 ml of filtrate. Furthermore the optical transmission of the filtrates was measured. The he Results are shown in Table 11.

Table 11

Claims (23)

1. A process for the preparation of water-soluble polymers containing ethyleneimine units with a narrower molar mass distribution, characterized in that from solutions of polymers containing ethyleneimine units with the customary broad molecular weight distribution by ultrafiltration on membranes, 5 to 95% by weight of polymers, based on the polymers used, separated off as permeate and the polymers containing ethyleneimine units with a narrower molar mass distribution, if appropriate, isolated from the retentate. 2. The method according to claim 1, characterized in that one 20th up to 90% by weight, based on the polymers used, as Separates permeate. 3. The method according to claim 1 or 2, characterized in that to ultrafiltration on membranes with a separation limit for polymers with molecular weights of 1000 to 1 million. 4. The method according to claim 1 or 2, characterized in that to ultrafiltration on membranes with a separation limit for polymers with molecular weights of at least 1000. 5. The method according to claim 1 or 2, characterized in that to ultrafiltration on membranes with a separation limit of at least 100,000. 6. The method according to any one of claims 1 to 5, characterized records that the membranes in the form of tubes, hollow fibers, plate devices or spiral winding modules and the Polymers containing ethyleneimine units as an aqueous solution uses solutions. 7. The method according to claims 1 to 6, characterized in net that the separated as permeate portions of Polyme ren for the synthesis of water-soluble, ethyleneimine units containing polymers with the usual broad molar mass division and these polymers again the Ultra subjected to filtration on membranes, wherein 5 to 95 wt .-% of polymers, based on the polymers used, as Separates permeate.   8. The method according to claim 7, characterized in that one the low molecular weight portions of Po separated as permeate lymeren reacted with ethyleneimine. 9. The method according to claim 7, characterized in that one the low molecular weight portions of Po separated as permeate lymeren with at least two functional groups Crosslinkers. 10. The method according to claim 7, characterized in that one the low molecular weight portions of Po separated as permeate lymeren first reacted with ethyleneimine and the he reaction products with at least two functional Group-containing crosslinkers to water-soluble, ethylenei polymers containing min units with the usual broad Molar mass distribution can react. 11. The method according to any one of claims 1 to 6, characterized records that one uses polyethyleneimines as polymers. 12. The method according to any one of claims 1 to 6, characterized records that one grafted as polymers with ethyleneimine Polyamidoamine uses. 13. The method according to any one of claims 1 to 6, characterized shows that reaction products are used as polymers, by grafting polyamidoamines with ethyleneimine and subsequent reaction with at least two functional groups pen-containing crosslinkers can be produced. 14. The method according to any one of claims 1 to 6, characterized in that reaction products are used as polymers, which are obtainable by reaction of Michaeladditionspro products

• - Polyalkylene polyamines, polyamidoamines, polyamidoamines grafted with ethyleneimine and mixtures of the named compounds and
• - Monoethylenically unsaturated carboxylic acids, salts, esters, amides or nitriles of monoethylenically unsaturated carboxylic acids, chlorocarboxylic acids, glycidyl acid, alkali salts of glycidyl acid and / or glycidyl acid amide

With
at least bifunctional crosslinkers. 15. The method according to any one of claims 1 to 6, characterized in that the polymers used are crosslinked, partially amidated polyethyleneimines which are obtainable by

• - Reaction of polyethyleneimines with
• - monobasic carboxylic acids or their esters, anhydrides, acid chlorides or acid amides

and if necessary

• - Implementation with at least two functional double bonds containing crosslinkers.

16. The method according to any one of claims 1 to 6, characterized records that as polymers quaternized polyethylene imine uses. 17. The method according to any one of claims 1 to 6, characterized records that one modifi as polymers by Strecker reaction adorned polyethyleneimines. 18. The method according to any one of claims 1 to 6, characterized records that one phosphonomethylated polyethyleneimines puts. 19. The method according to any one of claims 1 to 6, characterized is characterized in that the reaction products of poly uses ethylenimines with ketenes. 20. The method according to any one of claims 1 to 6, characterized records that as polymers alkoxylated polyethyleneimines starts. 21. Use of those obtainable according to claims 1 to 20 high molecular weight proportions of polymers as retention, drainage Fixing and fixing agent in the manufacture of paper, as Promoter in the sizing of paper with alkyldiketenes, as Flocculant for sewage sludge, as an adhesion promoter at Production of composite films, as an additive in hair and skin care products and as a means of immobilizing anioni active substances.