DE10310287A1 - Process for the preparation of polymeric condensates and their use - Google Patents

Abstract

Process for the preparation of polymeric condensates, characterized in that the reaction mixture is passed at least once through a zone of high energy density during the condensation reaction, which has an energy density of at least 10 · 5 · J / m · 3 ·.

Description

The invention relates to a method for producing polymeric condensates in particular of their aqueous solutions, the products thus obtainable and their Use.

In the production of polymeric condensates, in which the low molecular weight Shares are ineffective or only slightly effective for the intended application, one can try to determine the proportion of the higher molecular weight, effective polymers Increase the cost of ineffective, low molecular weight polymers. A possible one The way is to further condense these low molecular weight condensates.

The disadvantage here, however, is that the distribution of the Molecular weights also result in very high molecular weight polymers that do not Have more effectiveness because they tend to gel and / or fail. The latter properties make the polymer mixture largely unusable.

The way of condensation to has been described many times in the prior art to operate at the beginning of the gelling or the precipitations and the received Polymer mixture then from the ineffective, low molecular weight polymer fraction to be freed by means of membrane filtration (cf. WO-A 00/67 884, DE-A-196 00 366, US-A-6 056 967 and EP-A-873 371). The separated low molecular weight can then again fed to a polycondensation.

The disadvantage of this procedure is u. a. the wastewater load produced in the process.

It has now been tasked with an alternative manufacturing process for Polycondensates without providing the disadvantages of the prior art.

A process has now been found for producing polymeric condensates, which is characterized in that the reaction mixture is passed at least once through a zone during the condensation reaction which has an energy density of at least 10 ⁵ J / m ³ .

The condensates preferably produced by the process according to the invention are polycations and preferably have an average molecular weight of 0.7 to 1.5 Million g / mol.

The process according to the invention can be used for the preparation of anionic, neutral as well as cationic products are used. It can be continuous or be carried out discontinuously.

For example, the application of a correspondingly high energy density can be realized that the reaction mixture is continuously bypassed removed, passed through the zone of high energy density and then the reaction is returned again.

It is preferred that the reactor volume is circulated at least once. It is particularly preferred to circulate the reactor volume at least 4 times. there it is advantageous to use the energy supplied to apply the necessary energy dissipated by a heat exchanger in the bypass. It is particularly preferred install this heat exchanger in front of the mixing unit, so that Reaction medium is cooled before the zone of high energy density.

It is particularly advantageous to use the polycondensation required Dosing the reaction component also in the bypass. According to this variant are preferred Reaction temperature and temperature in the zone through flow heat exchangers set.

It is also possible to use a mixing unit that has the required energy input guaranteed to be installed in a reactor. The energy supplied can be after this Variant either via the cooling of the boiler jacket or via additional attached immersion cooler.

It is preferred to connect a cascade of reactors in series and the Condensation in the first reactor of the cascade as in a batch reaction up to now usual to carry out the reaction mixture under the high energy input into the to conduct second reactor and there the reaction, if necessary with addition to continue with further educt quantities. The dissipation of the energy introduced can be both via a heat exchanger before and / or behind the Mixing unit take place, as well as by cooling the boiler jacket or by a Immersion cooler.

This procedure can be repeated using additional cascade reactors.

Suitable mixing units are characterized by the fact that, owing to their Geometry has a high local energy density in the form of flow energy in the product enter. Since high pressures are often used for this task, they are used Mixing units also referred to as high-pressure homogenizers. Mixing units, which are particularly suitable for such tasks are static mixers and / or Jet aggregates. Simple perforated screens, flat nozzles, Jagged nozzles, knife edge nozzles, microfluidizers as described in US Pat. No. 4,533,254 Microstructure mixers, microstructure components or jet dispersers are described. Other geometries based on the same principle of this or another Nozzle units work are easily accessible to the expert. Using the example of a simple one Pinhole is explained the functional principle of these nozzle units. The Product flow is pressurized by a pump and expanded through the orifice. Due to the sudden cross-sectional narrowing, the product flow in the nozzle greatly accelerated. Depending on the geometry of the screen, two types of forces can arise act on the product. Either the product flow is accelerated so much that the flow in the nozzle is turbulent or, in the case of a laminar flow, a so-called expansion flow occurs in the nozzle.

In FIGS. 1 to 5 of DE-A 101 09 484 Other examples of suitable nozzles are shown aggregates. Fig. 1 shows a flat nozzle, in Fig. 2 a knife edge nozzle is shown, while in Fig. 3 a microfluidizer is shown. FIG. 4 shows a prong nozzle and FIG. 5 shows a jet disperser.

In addition to these mixing units, which have a high energy density in the form of Entering flow energy into the product are also suitable devices that have a bring high energy density through rotating parts, such as B. Rotor-stator systems, ball mills, colloid mills, wet rotor mills, Gear rim dispersing machines, intensive mixers, the principle of the gear rim dispersing machines use, however, flow in the axial direction, or other rotating Parts-using apparatus that are easily accessible to those skilled in the art and for which task can be used.

Furthermore, those mixing units should be mentioned, such as. B. Ultrasonic disintegrators generate high energy densities through cavitation. Under cavitation understood the formation and collapse of vapor bubbles in a liquid, in which an isothermal pressure drop initially up to the vapor pressure of the liquid takes place and the pressure then rises again. Because of the pressure increase the resulting gas bubbles collapse again. During the collapse process, the comminuting energy released. By adding a liquid with a suitable vapor pressure can therefore also in this way in the reaction product necessary energy density can be achieved.

In addition, combinations of the above or similar can be used Mixing units are used.

It has been shown that it is suitable for the production of polymeric condensates the method according to the invention is preferred, certain minimum values for Energy density and preferably also total residence times (product of residence time per Passage and number of passes) in the mixing unit must not be undercut.

In the case of the nozzle assemblies, the energy density E _v is determined by the pressure difference (homogenizing pressure) Δp _H effective at the nozzle:

E _v [J / m ³ ] = ΔP _H

For mixing units that work on the principle of rotor-stator systems, the energy density can be calculated experimentally from the power P introduced, the density ρ, the dispersing volume V _sp and the residence time t in this volume as follows:

E _v [J / m ³ ] = P × ρ ^-1 × V _sp ^-1 × t

The preferred shear energies are preferably at least 7.5 × 10 ⁶ J / m ³ , in particular at least 1 × 10 ⁷ J / m ³ . Nozzles with hole diameters from 0.1 mm to 5.0 mm, in particular from 0.1 to 2.0 mm, are preferably used.

The residence time of the product in the corresponding zones with high energy densities is preferably at least 1 × 10 ^-6 seconds, in particular 1 × 10 ^-5 to 1 second. The condensate or the reaction mixture is preferably passed once through at least one zone with a high energy density. As a rule, however, several passes through the mixing unit are realized.

The preferred solvent for the process according to the invention is water, however the process is basically independent of the solvent.

The high energy input takes place preferably at the reaction temperature but also at a different temperature. It is preferably carried out at 20 ° C to 150 ° C.

• - Kondensationsprodukte von Alkylendiaminen, von Polyalkylenpolyaminen, von mit Ethylenimin gepfropften Polyamidoaminen sowie von deren Mischungen mit mindestens zwei funktionelle Gruppen aufweisenden Vernetzern,
• - Kondensationsprodukte von Michaeladditionsprodukten aus Polyalkylenpolyaminen, aus Polyamidoaminen, aus mit Ethylenimin gepfropften Polyaminoaminen sowie deren Mischungen und monoethylenisch ungesättigten Carbonsäuren sowie deren Salzen, Estern, Amiden oder Nitrilen mit mindestens zwei funktionelle Gruppen aufweisenden Vernetzern,
• - amidierte Polyethylenimine, die erhältlich sind durch Reaktion von Polyethyleniminen mit einbasischen Carbonsäuren oder ihren Estern, Anhydriden, Säurechloriden oder Säureamiden und gegebenenfalls Kondensation der amidierten Polyethylenimine mit mindestens zwei funktionelle Gruppen aufweisenden Vernetzern,
• - Polyethylenimine, quaternisierte Polyethylenimine, phosphonomethylierte Polyethylenimine, alkoxylierte Polyethylenimine und/oder durch StreckerReaktion carboxymethylierten Polyethylenimine und
• - vernetzte alkoxylierte Polyethylenimine, vernetzte, quarternisierte Polyethylenimine, vernetzte phosphonomethylierte Polyethylenimine und/oder vernetzte durch Streckerreaktion carboxymethylierte Polyethylenimine sein können.

The process according to the invention is preferably characterized in that water-soluble (preferably> 1 g / l at 20 ° C.) and amino group-containing compounds are selected as condensates

• Condensation products of alkylenediamines, of polyalkylene polyamines, of polyamidoamines grafted with ethyleneimine and of their mixtures with crosslinking agents having at least two functional groups,
• Condensation products of Michael addition products from polyalkylene polyamines, from polyamidoamines, from polyaminoamines grafted with ethyleneimine and their mixtures and monoethylenically unsaturated carboxylic acids and their salts, esters, amides or nitriles with crosslinkers containing at least two functional groups,
• amidated polyethyleneimines which can be obtained by reacting polyethyleneimines with monobasic carboxylic acids or their esters, anhydrides, acid chlorides or acid amides and, if appropriate, condensing the amidated polyethyleneimines with crosslinkers which have at least two functional groups,
• - Polyethyleneimines, quaternized polyethyleneimines, phosphonomethylated polyethyleneimines, alkoxylated polyethyleneimines and / or carboxymethylated polyethyleneimines by Strecker reaction and
• - Crosslinked alkoxylated polyethyleneimines, crosslinked, quaternized polyethyleneimines, crosslinked phosphonomethylated polyethyleneimines and / or crosslinked carboxymethylated polyethyleneimines by stretching reaction.

• a) ethylengruppenenthaltenden Polyaminen oder deren Umsetzungsprodukten mit organischen, insbesondere aliphatischen oder aromatischen Dicarbonsäuren oder deren Derivaten, insbesondere Anhydriden, Estern oder Säurehalogeniden, aliphatischen oder aromatischen Diisocyanaten oder Alkylenoxiden, insbesondere Ethylenoxid oder Propylenoxid, mit
• b) Aminvernetzern, insbesondere 1,2-Dichlorethan, 1,2-Dibrommethan, 1,3-Dibrompropan, 1-Chlor-3-Brompropan und Epichlorhydrin.

Cationic polyethyleneimines or polyamidoamines are also preferably produced as condensates by the process according to the invention and can be obtained by reacting

• a) Polyamines containing ethylene groups or their reaction products with organic, in particular aliphatic or aromatic dicarboxylic acids or their derivatives, in particular anhydrides, esters or acid halides, aliphatic or aromatic diisocyanates or alkylene oxides, in particular ethylene oxide or propylene oxide
• b) amine crosslinkers, in particular 1,2-dichloroethane, 1,2-dibromomethane, 1,3-dibromopropane, 1-chloro-3-bromopropane and epichlorohydrin.

The preferred polyamine of component a) is one of the formula (I)

H ₂ NA-NH ₂ (I),

wherein
A for a bivalent radical of the formula

- (CH ₂ CH ₂ N (R)) _n CH ₂ CH ₂ -

stands with n = 0 to 50 and R independently of each repeating unit n stands for H, CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ NRH or for - (CH ₂ CH ₂ N (R)) _q , where q stands for is a number from 0 to 50 and R can have the above meaning independently of each repeating unit.

Particularly preferred polyamines of component a) are diethylene triamine, Triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, N-methyldipropylenetriamine or higher condensed, linear or branched components or Mixtures of these compounds.

Polyamine mixtures or their corresponding reaction products are also preferred as component a). Particularly suitable polyamine mixtures are those which
20 to 80% by weight of hexamines,
up to 50% by weight of pentamines,
up to 30% by weight tetramine,
up to 10% by weight of low-volatile amines smaller than tetramines, in particular diethylenetriamine, ethylenediamine and aminoethylpiperazine,
5 to 20% by weight of heptamines to dodecamines,
up to 30% by weight higher amines than dodecamines
contain.

Hexamine means pentaethylene hexamine or the corresponding branched analog. The other names follow this system.

Preferred made from the ethylene group-containing polyamines Reaction products are preferably reaction products of the polyamines with at least one bifunctional crosslinkers with the formation of neutral intermediates.

Such bifunctional crosslinkers can be: aromatic or aliphatic Dicarboxylic acids, such as. B. terephthalic acid, succinic acid, adipic acid, sebacic acid, aromatic or aliphatic diisocyanates, such as. B. hexamethylene diisocyanate, p- Phenylene diisocyanate, ethylene oxide, propylene oxide or compounds with different functional groups, such as. B. acrylamide or acrylic acid or half-sided reaction products of other bifunctional reagents, e.g. B. Di- or Polyamines or of di- or polyethylene glycols with these crosslinkers.

Trifunctional crosslinkers are also suitable, such as cyanuric chloride, Triisocyanates or maleic anhydride.

Preferred components a) are reaction products of polyamines with aliphatic dicarboxylic acids to polyamide amines.

The preferred polyamide amines of component a) are understood to be the derivatives of the polyamines with dicarboxylic acids, in particular aliphatic C ₃ -C ₁₀ dicarboxylic acids (such as succinic acid, adipic acid or sebacic acid or aromatic C ₈ -C ₁₅ dicarboxylic acids such as terephthalic acid), with adipic acid being particularly preferred is.

Preferred polyamide amines of component a) have the formula (II)

H ₂ N-OC (CH ₂ ) _m CONH (A-NHOC (CH ₂ ) _m CO) _p NH ₂ (II),

wherein
A has the above meaning and
m represents 1 to 8, in particular 4, and
p stands for a number from 1000 to 10000.

A compound is preferably used under amine crosslinker of component b) understood, which is able to form two amino groups with the formation of quaternary salts to network.

Such crosslinkers can e.g. B. dihaloalkanes such as 1,2-dichloroethane, 1,2-dibromomethane, 1,3-dibromopropane or epichlorohydrin or the half-sided Implementation products of these bifunctional reagents with as a bridge components used, e.g. B. di- or polyamines or di- or polyglycols with these Be a networker.

• A) Aldehyden und/oder Ketonen und gegebenenfalls
• B) einer oder mehreren Verbindungen, ausgewählt aus der Gruppe der nicht sulfonierten Aromaten, Harnstoff und Harnstoffderivaten.

Also preferred as condensates are condensation products based on

• A) aldehydes and / or ketones and optionally
• B) one or more compounds selected from the group of unsulfonated aromatics, urea and urea derivatives.

The invention further relates to those according to the method of the invention available condensates.

Furthermore, the invention relates to the use of the invention or condensates obtained by the process according to the invention as retention, Filtration, drainage and fixing aids in the manufacture of paper, as Wet strength agent for paper, as a promoter in the sizing of paper Alkyldiketenes or alkyl succinic anhydrides, as flocculants for sewage sludges, as Adhesion promoter in the production of composite films, as an additive in hair and Skin care products, as a means of immobilizing anionic active ingredients and as a means of improving the authenticity of textile dyeings.

example 1

• a) 1053 g of an amine mixture of 10% tetraethylene pentamine, 5% triethylene tetramine, 47% pentaethylene hexamine, 13% higher boiling and 25% non-volatile amines are condensed with 461.3 g adipic acid at increasing temperature up to 170 ° C with distilling off water of reaction.
  The resulting polyamide amine is discharged onto 1514 g of water and transferred to a pressure reactor.
• b) 585 g of the amine solution from Example 1a) are diluted with 470 g of water and at a reaction temperature between 100 ° C and 130 ° C with about 15 g Dichloroethane condensed. The dichloroethane becomes so in about 6 hours added that an increasing viscosity can be observed well. As soon as a sharp increase in viscosity occurs, the dosage is reduced canceled. By relieving the excess pressure, excess becomes Dichloroethane removed. To remove all low volatile components, the Reaction mixture transferred to a pre-evacuated reactor. That included distilled water is added again after cooling. You get one light yellow solution with a solids content of 30% and a viscosity 500 mPas.
• c) The reaction product from Example 1b is at a pressure of 500 bar pressed through a nozzle with a diameter of 0.2 mm. It drops the viscosity to a value of about 250 mPas. The sheared product is again at 120 ° C with dichloroethane to a viscosity of 500 mPas condensed.
• d) The reaction product from Example 1c is used as in c) described.
• e) Repeat the procedure under c) 4 times each with that from the reaction mixture obtained in each precursor.

Example 2

The application-related effectiveness of those according to Examples 1b) to 1e) Polymers produced in a generally known manner by measuring the Accelerated drainage rate determined.

A pulp with a consistency of 3 g / l was produced from 100 parts of unprinted waste paper with a filler content of 10%. 10% China Clay Grade B was used as filler. Another additive was 0.5% alum. The pH of the pulp was 7.2. The paper stock was divided into several portions, which were then mixed with 0.1%, 0.2%, 0.3%, 0.4%, 0.5% and 0.6% retention aid. The acceleration of the dewatering rate of the 6 concentrations was arithmetically averaged to an "overall effectiveness". Example 1a here is a reference sample and was set to 100%.
Example 1a 100%
Example 1b 117%
Example 1c 124%
Example 1d 126%
Example 1e 131%
Example 1e (repeated twice) 135%
Example 1e (repeated 3 times) 138%
Example 1e (repeated 4 ×) 142%

It clearly shows that the effectiveness of the drainage aids after The inventive method can be significantly improved.

Example 3

In a cascade of 7 reactors with a dosing option for dichloroethane and an online viscosity measurement is equipped with a Dosing speed of 0.9 liters / hour a 24% solution of a Polyamine amide melt pumped in continuously according to Example 1a. The reaction temperature will kept at 120 ° C in all reactors. At the same time dichloroethane is in the Reactors metered. The dosing rate is regulated so that a Set viscosity between 200 mPas and 400 mPas. When transferring the Reaction mixture in the next kettle is at a pressure of at least 300 bar pressed through a nozzle system with a hole diameter of 0.2 mm. In the third and in the seventh reactor an additional 150 ml of water per hour metered.

After passing through the seventh reactor, a pre-evacuation is carried out Degassed collection container. The azeotropically distilling, unreacted dichloroethane can Process again. The solids content of the end product is reduced to 20% set.

A product with an equal effectiveness of 140% is obtained.

Comparative Example 4

If the reaction product from Example 1b is subjected to membrane filtration, products with a comparable increase in activity are obtained.

To reduce the viscosity, membrane filtration was carried out at one temperature of 60 ° C.

To avoid clogging of the membrane, the product had to be Membrane filtration can be diluted to a concentration of 15%. From 20 kg Starting goods were obtained 8.6 kg final concentrate at a concentration of 12.7%, as well 50 kg permeate with a concentration of 3.8%.

Before returning the permeate to a new condensation according to example 1b it must be concentrated again to a concentration of 25%. there approx. 45 kg of waste water is generated.

Claims (11)

1. A process for the preparation of polymeric condensates, characterized in that the reaction mixture is passed at least once through a zone of high energy density during the condensation reaction, which has an energy density of at least 10 ⁵ J / m ³ . 2. The method according to claim 1, characterized in that the zone is higher Energy density is passed through at least twice. 3. The method according to claim 1, characterized in that the energy density is at least 7.5 × 10 ⁶ J / m ³ . 4. The method according to claim 1, characterized in that the energy density is at least 1 × 10 ⁷ J / m ³ . 5. The method according to claim 1, characterized in that water-soluble and amino group-containing compounds are selected as condensates Condensation products of alkylenediamines, of polyalkylene polyamines, of polyamidoamines, of polyamidoamines grafted with ethyleneimine and of their mixtures with crosslinking agents which have at least two functional groups, Condensation products of Michael addition products from polyalkylene polyamines, from polyamidoamines, from polyaminoamines grafted with ethyleneimine and their mixtures and monoethylenically unsaturated carboxylic acids and their salts, esters, amides or nitriles with crosslinkers containing at least two functional groups, amidated polyethyleneimines which can be obtained by reaction of polyethyleneimines with monobasic carboxylic acids or their esters, anhydrides, acid chlorides or acid amides and, if appropriate, condensation of the amidated polyethyleneimines with crosslinkers having at least two functional groups, - Polyethyleneimines, quaternized polyethyleneimines, phosphonomethylated polyethyleneimines, alkoxylated polyethyleneimines and / or carboxymethylated polyethyleneimines by Strecker reaction and - Crosslinked alkoxylated polyethyleneimines, crosslinked, quaternized polyethyleneimines, crosslinked, phosphonomethylated polyethyleneimines and / or crosslinked carboxymethylated polyethyleneimines by Strecker reaction. 6. The method according to claim 1, characterized in that cationic polyethyleneimines are prepared as condensates, obtainable by reacting a) Polyamines containing ethylene groups or their reaction products with organic, in particular aliphatic or aromatic mono- or dicarboxylic acids or their derivatives, in particular anhydrides, esters or acid halides, aliphatic or aromatic mono- or diisocyanates or alkylene oxides, in particular ethylene oxide or propylene oxide b) amine crosslinkers, in particular 1,2-dichloroethane, 1,2-dibromomethane, 1,3-dibromopropane, 1-chloro-3-bromopropane and epichlorohydrin. 7. The method according to claim 6, characterized in that the polyamine of component a) is that of formula I.

H ₂ NA-NH ₂ (I),

wherein
A for a bivalent radical of the formula

- (CH ₂ CH ₂ N (R)) _n CH ₂ CH ₂ -

stands with n = 0 to 50 and R independently of each repeating unit n stands for H, CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ NRH or for - (CH ₂ CH ₂ N (R)) _q , where q stands for is a number from 0 to 50 and R can have the above meaning independently of each repeating unit. 8. The method according to claim 1, characterized in that the high Energy density continuously or discontinuously on the reaction mixture acts. 9. The method according to claim 1, characterized in that the high Energy density with a viscosity of the reaction mixture greater than 200 mPas is carried out. 10. Polymeric condensates obtainable according to at least one of the preceding Expectations. 11. Use of the polymeric condensates according to claim 10 as filtration, Dewatering and fixing aids in the manufacture of paper as Promoter in the sizing of paper with alkyldiketenes or Alkyl succinic anhydrides, as flocculants for sewage sludges, as adhesion promoters in the production of composite films, as an additive in hair and Skin care products, as agents for the immobilization of anionic active substances and as Means for improving the authenticity of textile dyeings.