DD268832A3 - METHOD FOR PRODUCING HYDROLYZING POLYCATION COMPOUNDS - Google Patents

Abstract

The invention relates to a process for the preparation of polyesteramines and / or polyesteramidamines in which polycationic compounds of the general formula are obtained via nucleophilic addition of low molecular weight compounds. A new and at the same time simple process for the preparation of polycationic hydrolyzing polyesteramines and / or polyesteramidamines gives substances which are used as precipitants or flocculants for biotechnological separation processes, for wastewater treatment and for the cationization of materials. formula

Description

Alkylene, phenylene, arylene R, ₂ , R, ₃ ... alkyl, allyl, hydroxyalkyl

-Cx NR ₄ R ₅ ; -Cx-phenyl; -Cx-aryl-CH ₂ -CHR ₆ -COOR ₇ ; -Cx-O-CO-C = CH ₂

R ₆

g, h, i, k ... 2 to 5 I, m ... Obis 5

be seized.

4. The method according to claim 1 to 3, characterized in that diamines and / or polyamines and / or oligoamidamines with α, ω-terminal, proton-bearing amino groups with di- (meth) acrylic acid ester compounds in the ratio of terminal amino groups to acrylate of 0.8 : 1 to 1: 0.8, preferably 1: 1, optionally with the addition of acid to the equimolar ratio to the amino groups to linear, hydrolyzing polyesteramines and / or Polyesteranidaminen at reaction temperatures up to 10O ⁰ C, preferably to 5O ⁰ C implemented become.

5. Process according to Claims 1 to 4, characterized in that water-soluble compounds are used as starting materials or their hydrolysis products.

6. The method according to claim 1 to 5, characterized in that the polyester amines or the Polyesteramidamine are soluble in water or go with the addition of up to equimolar amounts of acid in solution.

7. The method according to claim 1 to 6, characterized in that the polyester amines and / or the polyester amides are reacted according to known methods to corresponding ammonium salts.

8. The method according to claim 1 to 7, characterized in that in the

Polyesteramidaminverbindungen 0.1% to 99% ester bonds, preferably 1 to 30%, based on the sum of ester and amide bonds present.

Field of application of the invention

The invention relates to a process for the preparation of hydrolyzing polycationic compounds which are suitable as flocculants in a wide range of economics, but in particular for biotechnologies but also for the clarification of waste water and in papermaking and as components for membrane and symplex formation. These compounds can be used wherever polyamidoamines are currently used.

-3- 268 832 characteristic of the known prior art

It is known to use polyamidoamines, substituted poly- and copolyacrylic esters, poly- and copolyacrylamide compounds, polyalkyleneimines and polydimethyldiallylammonium chlorides as flocculating agents, etc. (Polyelectrolytes for Water and Waste Water Treatment, USA, CRC-Press, 1981). These bubstanzen represent permanent, hydrolytically difficult to biodegrade, polycationic polymers that accumulate over time in nature and are usually highly toxic to fish when they are used in flours for flocculation ι: 'id so enter the waters. Although they are very well suited for bio-protein flocculation, they lead to disturbances in the gastrointestinal tract when feeding de-flocculated organic protein to animals. According to CH-PS 606133 pendant type polycations as retention agents u. a. described in the purification and purification of waste water, in which the cationic charge as a side chain to the non-biodegradable copolyacrylamide as a base polymer depends. With the cleavage of the biodegradable fragments, the polycation loses its properties while retaining the backbone.

Object of the invention

The aim of the invention is to develop polycationic polymers with predetermined breaking points, which decompose hydrolytically in the aqueous medium after use, d. H. lose their polycation effect and easily hydrolyze to barely odor non-toxic substances.

Explanation of the nature of the invention

According to the invention, this object is achieved in that substituted di- or polyamines and / or oligomeric Amidaminverbindungan in the molecular weight range up to 10,000, preferably 5000, with proton-bearing amine end groups with α-, ß-unsaturated, polar di- or polyolefin compounds in water and / or a solvent or solvent mixture via nucleophilic addition to linear or branched hydrolyzing polycationic polyesteramine and / or polyesteramidoamine compounds having the general formula:

~ CHR - CO - 0 .- (NX) ^> ₀ ^ 0 - CO - CHR - CH ₂

-Y- NY ~ (NZ). > "NY L LcO <~ (NZ ')

T t- ° i { ₌ 0 or 1 ^L

Jr; JF;

CO - (NZ ")> ₀ ~ CO - NY ~ (NZ) ^ ₀ ~ NY

be implemented. It is advantageous, as substituted di- or polyamines, the compounds having the structure

and or

"4 Ν- (CIl ₂ ) _e f N -R ₃

R ₁₁ R ₂ ... -H; alkyl; allyl

-Cx NR ₄ R ₅ ; -Cx-phenyl-Cx-aryl; Hydroxyalkyl -CH ₂ -CHR ₆ -COOR ₇

R ₃ ... -Hi τ (CH ₀ ) N -H. - L * ^{e 1} J R ₄₁ R ₆ ... -H; alkyl; allyl; Cx-phenyl Hydroxyalkyl; -CH ₂ -CHR ₆ -COOR ₇ R ₆ ... -H; Alkyl; -Cx-CN -Cx-phenyl; -Cx-aryl -Cx COOR ₇ R ₇ ... -H; Alkyl; -Cx-phenyl Hydroxyalkyl; -Cx-NR ₄ R ₆ from... 0.2 to 4; if a = 0, then b Φ 0 c, d, e, f ... Obi 10 -Cx .. Alkylene with χ CH ₂ units

directly or with the compounds Ci ^ = C-COOR ₇

and / orR ₇ -O-CO-R ₁₀ -CO-OR ₇

Rio · .. alkylene, phenylene, arylene

to oligomer amidamine Vei compounds via a well-known addition and / or transesterification and / or condensation reaction to implement so that terminal amine end groups arise. These compounds are then in the polymer synthesis reaction by nucleophilic addition of the NH groups at reaction temperatures up to 10O ⁰ C, preferably to 5O ⁰ C, with (meth) acrylic acid ester compounds of the structure:

CH ₂ = C-CO-O-Ru-O-CO-C = CH ₂

R ₈ ¹ R ₆

- (CH ₂ ) g- | N ¹

< ^CH 2> b

- (CH ₂ )

₂ ) _c -

N-

and or

and or

Ί2 m

alkylene; phenylene; arylene

alkyl; Allyl; -Cx-NR ₄ R ₆

hydroxyalkyl

-Cx-phenyl; -Cx-aryl-CH ₂ -CHRe-COOR ₇ -Cx-O-CO-C = CH ₂

Re g, h, i, k ... 2 to 5 l, m to 0 to 5

use.

Linear hydrolyzing polyesteramines and / or polyesteramidamines are obtained when diamines and / or polyamines and / or oligoamidamines having α, ω-terminal, proton-carrying amino groups with di (meth) acrylic acid ester compounds in the ratio of torminal amino to acrylate groups of 0, 8: 1 to 1: 0.8, preferably 1: 1 reacted. Depending on the choice of Raaktanten and the reaction conditions linear or branched polyester amines and / or polyester amidamines are obtained when di- or polyamines and / or Oligoamidamine with primary

Amine end groups and secondary amino groups with di- and / or Polyesterverbindunyen the (meth) acrylic acid are reacted together. The degree of branching can be controlled by the addition of acid, preferably saturated or sulfuric acid. Since the polyesteramines and Polyesteramidamine are sensitive to hydrolysis, the reaction products must be used after the synthesis without prolonged storage. It is advantageous to carry out the synthesis in a stirred vessel or a vessel with a mixing device directly before use, wherein the polyamine and / or the oligoamidoamine compound is preferably stored dissolved in water, and the di- or polyester of the (meth) acrylic acid in Substance or in an organic inert solvent oJer solvent mixture is stored depending on the structure and solubility in the presence of a Polymerisationsinhihitors. Preferably, the di- or polyester compound of (meth) acrylic acid in the l'olyamin- and / or oligoamidamine slowly added with stirring. After completion of the reaction, the reaction solution can be used directly. With the addition of equimolar amounts of acid, the corresponding ammonium compounds are formed.

On the choice and the variation of the composition, i. about the structure of the polyester. amine and / or Polyesteramidaminverbindungen the hydrolysis rates of the polycations can be adjusted by the concentration of defined predetermined breaking points.

The polycations hydrolyze after use as a "precipitant or flocculant over a defined hydrolytic degradation in the aqueous medium with cleavage of the main chain in less or hardly toxic fragments with loss of polycation, since both the molecular weight and the charge density and aie charge density distribution of crucial importance the polycation effect.

By the proposed solution known polycationic, permanent or difficult to hydrolyze, linear or branched polyamines or polyamidoamines are modified so that new products are obtained with the qualitatively new property of the defined degradation over predetermined breaking points.

embodiments

General procedure for the synthesis of the polyesteramine and polyesteramidoamine compounds (preferably linear products):

Example 1: Linear Polyketenes

Secondary diamine, substituted polyamine having terminal secondary amino groups or oligoamidoamine with 0.5 molar secondary amino end groups are reacted with 0.5 molar vinyl units of a diester with acrylic acid (diacrylate) with stirring in water with cooling by charging the amine component in water and slowly adding, with stirring, the diester of acrylic acid diluted in an inert solvent. After completion of the exothermic reaction is stirred for up to 1 hour at room temperature.

Example 2: Linear or Branched Polycations

Diamine, polyamine and oligoamidoamine with primary, α, ω-terminal amine end groups are initially introduced in a concentration of 0.5 mol of primary, α, ω-terminal amine end groups in water. Depending on the desired degree of branching, 0.5 + X base moles of vinyl units of the preferably used diester of acrylic acid can be reacted while stirring in water with cooling. The diester of acrylic acid is added diluted in an inert solvent. With the addition of mineral acid to the amine to equimolar amounts of amine moieties, the degree of branching can also be controlled. After completion of the exothermic reaction is stirred for a further 1 hour.

Following the above instructions, the following products were converted to polyesteramine and polyesteramidoamine compounds:

- Amine components:

(A) Ethylenediamine

(B) diethylenetriamine

(C) dipropylenetriamine

(D) Ν, Ν-dimethylamino-n-propylamine

(E) piperazine

(F) N, N'-dimethylethylenediamine and derivatives of the structure derived therefrom

H - N +

CH ₂ - CH ₂ -

^CH 3 Ιί »ί 10

(G) N'-Allyldipropylenetriamine (H) Oligomers of Polyethyleneimine (M <10000)

Cocomponent for the formation of oligoamidamine: (meth) acrylic acid methyl ester (meth) acrylic acid phenyl ester adipic acid and its esters

Component for the Nucleophilic Addition Chain Construction Reaction:

(I) Ethylenediacrylic ester (ethylene diacrylate)

(II) N-methyl-N, N-di (ethylene-acrylic ester) amine

(III) N, N'-dimethyl-N, N'-di (ethylene-acrylic ester) ethylenediamine

(IV) N.N'-dKethylenacrylesterJpiperazin and the Methacrylesterderivate

By co-condensation with the oligoamidoamines and the co-addition, the hydrolysis properties of these polyesteramines and polyesteramidamines can be set in a defined manner.

The compounds described introduce polycations of the integral type. These cationic polymers carry charge directly in the ketla and degradation of the polycations occurs with cleavage of the backbone into fragments that have less or no toxic effect and further biodegrade to less or nontoxic compounds.

Claims (3)

1. A process for the preparation of polyester amines and Polyesteramidamineri, characterized in that substituted di- or polyamines and / or oligomeric amide amine compounds in the molecular weight range up to 10000, with proton-bearing amine end groups with α, ß-unsaturated, polar di- and / or Polyolofinverbindungen to linear or branched hydrolyzing polycationic polyesteramine and / or polyesteramidoamine compounds having the general formula: CH ₂ - GHR - GO - 0 ~ (WX) ^> ₀ ^ 0 - CO - CHR - CH ₂ -L ^co ~ Z o ^OT be implemented. 2. The method according to claim 1, characterized in that as substituted di- or polyamines compounds having the structure II-4-N _v \ ^a y N - (CH ^) _n H Nv. \ ^a ) N - H L ^V (CH ₂ ), and or ^H ff - ^ Ve-hr- ¹ / - R ₁ , R ₂ ... -H; alkyl; allyl; hydroxyalkyl -Cx NR ₄ R ₅ ; -Cx-Phenyl-Cx-Aryi; -CH ₂ -CH-COOR ₇ R ₆ R ₃ ... -H; j (CH ₂ ) _e - NjH LR ₁ f R ₄ , R ₅ ... -H; alkyl; allyl; hydroxyalkyl -Cx-phenyl; -CH ₂ -CH-COOR ₇ R ₆ R ₆ ... -H; Alkyl; -Cx-CN; -Cx-phenyl -Cx-aryl; -Cx-COOR ₇ R ₇ ... -H; Alkyl; -Cx-phenyl -Cx NR ₄ R ₅ ; Hydroxyalkyl a, b ... 0.2 to 4 if a = 0, then b4 = 0 c, d, e, f ... Obis 10 -Cx ... AlkylenmitxCH ₂ units be used directly or with the connections CH ₂ = C-COOR ₇ R ₆ and or R ₇ -O-CO-Ri (T-CO-OR ₇
With Rio ... alkylene; phenylene; arylene be converted by known addition and / or transesterification and / or condensation reactions to oligomer-amidamine compounds having terminal proton-bearing amine end groups. 3. The method according to claim 1 and 2, characterized in that as α, ß-unsaturated, polar Dioder polyolefin compounds (meth) acrylic acid ester compounds of the structure CH ₀ = C - CO-OR .. -O-CO -C = CII. ₉ ^R 6