DD268357A3 - METHOD FOR PRODUCING HYDROLYZING POLYCATION COMPOUNDS - Google Patents

Abstract

A process for the preparation of polyesteramines is described in which condensation of low molecular weight compounds of the general formula HO (NXn) 1 gives COOR-hydrolyzing polycationic polyesteramines which swell and / or dissolve in the p H range 7 in water. The aim of the invention is to develop a new and at the same time simple process for the preparation of hydrolyzing polycationic polyester amines, which have significance as flocculants for wastewater treatment, for biotechnologies, for the symplex and membrane chemistry as well as for the cationization of materials.

Description

H 4 O - CH - GH R ₁ R ₂

- A _b »B ₀ - A _d - (CH ₂ ), £ CH - CH ₂ COOR,

/ (0H ₂ )

J;> - («v _m y <

< ^CH 2> k

R1 / R2 ... R3 »R4 ... R ₅ ... Rs / R7 ... R ₈ ; R ₉ ... a ... b, c, d , F, i, o ... e, g, h , m, n, x

-H; alkyl; hydroxyalkyl

-H; Alkyl; -C _x -CN; -C _x -COOR ₅

-H; alkyl; phenyl; hydroxyalkyl

alkyl; allyl; hydroxyalkyl; -C _x -COOR ₆ ; -C _x -phenyl; -C _x -Ary!

-C _x NR ₈ R ₉

alkyl; allyl

1 to 5

OodeM

0 to 5 k, 1 to 0.2 to 4, if k = 0

then I ^ OC _x ... AlkylenmitxCH ₂ units

3. ancestors according to claim 1 and 2, characterized in that the N- (2-Hydroxya! Kyl) amino acids or their ester derivatives at condensation temperatures up to 290 ⁰ C, preferably heated to 260 ⁰ C, under Sauerstoffau'jschluß and at reduced pressure , condensed to homo-, co- or terpolymers with a defined degree of branching and eliminated as a solid product.

4. The method according to claim 1 to 3, characterized in that as N- (2-hydroxyalkyl) amino acids or their estates! d jrivate or as hydrolysis products of N- (2-hydroxyalkyl) -amino acids or their ester derivatives in water-soluble compounds can be used.

5. The method according to claim 1 to 4, characterized in that the polyester amines are dissolved with equivalent amounts of acid in water.

6. The method according to claim 1 to 4, characterized in that the polyester amines are reacted by known methods to corresponding: ammonium salts.

Field of application of the invention

The invention relates! a process for the preparation of ₍ hydrolyzing polycationic compounds which are suitable as flocculants in a wide range of economics, but especially for biotechnologies, but also for the treatment of wastewater and paper production and as components for membrane or Symplexbildung suitable.

Characteristic of the known technical solutions

It is known to use polyamidoamines, substituted poly- and copolyacrylic esters, poly- and copolyacrylamide fonnings, polyalkyleneimines and polydimethyldiallylammonium chlorides as flocculants, etc. (Polyelectrolytes for Water and Waste Water Treatment, USA, CRC-Press, 1981). These substances are permanent, hydrolytically difficult to degrade, polycationic polymers that accumulate si-.h over time in nature and are usually highly toxic to fish when they are used in flours for flocculation and so get into the waters.

Although they are very well suited for feeding with egg whites, they lead to disturbances in the gastrointestinal tract when feeding the flaked bio protein to animals.

According to CH-PS 606133, counterpart type polycations are used as retention average u.a. described in the purification and purification of waste water, in which the cationic charge as a side chain to di m biologically non-degradable 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 object of the invention is to develop polycationic polymers which decompose hydrolytically in the aqueous Miliou after use, i. lose their Polykationwirkung and easily hydrolyze to barely or non-toxic substances.

Explanation of the essence of the invention

The invention has for its object to provide by using more suitable starting materials, a new class of Polykatipnen.

According to the invention the object is achieved in that tertiary N- (2-hydroxyalkyl) -substituted amino acids and / or their ester derivatives of the general formula

HO- (NX) _n *, - COOR

be transposed to polyester amines according to known transesterification and / or condensation reactions. As N- (2-HydroxyalkyD-amino acids or their ester derivatives are used, the compounds

H {θ -OH - CH} _a A _b - B _c - A _d - (Ott,) ,, £ OH - OH ^ - COOR ₅ R ₁ R ₂ R ₃ R ₄

with A. ·. -J-N - (CH -.) J-f n)

L ι * Λ ^V ! i

B.,

I ί * Γ! Η "> _ ^fc " ¹ Jn L ffiW _} _ 'J

R ,, R2 ... -H; alkyl; hydroxyalkyl Ra, R4 ... -H; alkyl; -C _x -CN; -C _x -COOR ₆ R ₆ ... -H; alkyl; phenyl; hydroxyalkyl Re, R7 ... alkyl; allyl; hydroxyalkyl; -C _x -COOR ₆ ; -C _x -phenyl; -C _x -aryl -C _x NR ₈ R ₉ Re / Re ··· alkyl; allyl a ... Ibis 5 b, c, d, f, i, o ... O or 1 e, g, h, m, n, x, .. O to 5 k, l ... 0.2 to 4; ifk = 0 dannl ^ O C _x ... Alkylene with χ CH ₂ units

It is advantageous to heat the N- (2-hydroxyalkyl) amino acids or their ester derivatives to condensation temperatures up to 290 ° C, preferably to 26O ⁰ C, with exclusion of oxygen and at reduced pressure to homo-, co- or Terpolyrreren with a defined Condensation to condense and eliminate as a solid product. An embodiment of the invention provides that the starting materials or their hydrolysis products are soluble in water.

The thus obtained: polycationic polyester amine compounds are stored in substance with exclusion of water indefinite, but must be brought before use with ac equivalent amounts of acid in water in solution. However, the corresponding ammonium salts can also be prepared from the polyesteramides prepared by processes known per se, stored and dissolved in aqueous media without further additions. The starting materials are readily prepared from commercial chemicals via nucleophilic substitution, nucleophilic addition o ^ he synthesized alkoxylation reactions with epoxide j ^n.

embodiments The invention will be explained in more detail below with reference to several exemplary embodiments.

0.1 mol of product is slowly heated to 220 ° C. with stirring in a reaction vessel under exclusion of oxygen and nitrogen gassing and optionally with the addition of a transesterification catalyst, and the resulting volatile

Product distilled off. After completion of the precondensation, the temperature is reduced to 29O ⁰ C under reduced pressure

elevated. The condensation is over when no volatile product is produced.

Depending on the type of substance is formed after cooling, a tough or rubbery or solid polymer mass, which in aqueous Media with addition of equivalent amounts of acid dissolves. Final products were quantitatively used for the reaction:

a) N-methyl-N- (2-hydroxyethyl) -e-aminocaproic acid

b) N-methyl-N- (2-hydroxyethyl) -β-aminopropanoic acid methyl ester, (2-hydroxyethyl) ester

c) N-methyl-N- (2-hydroxyethyl) -β-amino- (α-methylpropanoic acid) methyl ester

d) N-methyl-N- (2-hydroxyethyl) -glycine

e) N, N-di- (2-hydroxyethyl) -e-aminocaproic acid

f) N, N-di- (2-hydroxyethyl) -β-aminopropanoic acid-methyl ester-i2-hydroxyethyl) ester

g) N, N-di- (2-hydroxyethyl) -β-amino- (α-methylpropanoic acid) -methylester h) N, N-di- (2-hydroxyethyl) -glycine

i) N-Allyl-N- (2-hydroxyethyl) -β-aminopropanoic acid methyl ester (2-hydroxyethyl) ester

k) N-Allyl-N- (2-hydroxyethyl) -β-amino- (α-methylpropanoic acid) -methyl ester

I) N-allyl-N- (2-hydroxyethyl) -glycine

m) N-Allyl-N- (2-hydroxyethyl) -c-aminocaproic acid

n) Piperazi: o-N- (2-hydroxyethyl) -N'-propanoic acid methyl ester (2-hydroxyethyl) ester

o) Piperazino-N- (2-hydroxyethyl) -N '- (α-methylpropanoic acid) -methyl ester

p) piperazino-N- (2-hydroxyethyl) -N'-ethanoic acid and the Methylasterdei ivat

q) N- (2-hydroxyethyl) amino-.beta., .beta.-dipropanoic acid methyl ester (2-hydroxyethyl) -ester

r) N- (2-hydroethyl) amino-ß, ß'-di (a-methylpropanoic acid methyl ester

s) N- (2-hydroxyethyl) amino diethanoic acid and the methyl ester derivative

In addition to the polycondensation to the pure homopolyester amines were co- and Terpolyesteramine with the above

produced substances produced.

While the products a) to d) and i> to p) gave linear polyesteramines, in the homocondensation of e) to h) and

q) to s) branched or crosslinked ^r roducts on. The products e) to h) and q) to s) can be used in the co- and terpolycondensation, optionally defined as branching or crosslinking agents.

Furthermore, analogously to the N- (2-hydroxyethyl) derivatives in a) to s), the N- (2-hydroxypropyl) derivatives and also in a)

to d) polycondensed instead of the N-methyl and the N- (n-butyl) derivatives.

The obtained polycationic polymer end products are swellable in water in the pH range S7 and / or dissolve. The

products obtained are stable in substance and autocatalytically hydrolyzed in aqueous media, depending on the conditions and by the choice of the starting materials-related structure with cleavage of the main chain and thus lose their polykationische effect and toxicity. in the neutral range, degradation to nontoxic compounds occurs within a few hours to about 60 days.

The compounds described introduce polycations of the integral type. These cationic polymers carry their charge

directly in the chain and the degradation of the polycations takes place with cleavage of the main chain into fragments which have a lower or no toxic effect and further biodegrade too little or non-toxic compounds.

Claims (2)

claims: 1. A process for the preparation of hydrolysierenden polycationic Verbindunqen, characterized in that tertiary N- (2-hydroxyalkyl) -substituted amino acids and / or their ester derivatives of the general formula HO- (NX) ₁ ^ ₁ -COOR be converted into polyester amines according to known transesterification and / or condensation reactions. 2. The method according to claim 1, characterized in that as N- (2-hydroxyalkyl) amino acid or its ester derivatives, the compounds