DD268833A3 - METHOD FOR PRODUCING HYDROLYZING POLYCATION COMPOUNDS - Google Patents

Abstract

The invention relates to a process for the preparation of polyester amidamines in which over polycondensation of low molecular weight compounds hydrolyzing polycationic polyester amide amines of the general formula are obtained which swell or dissolve in the p H range 7 in water. A new and at the same time simple process for the preparation of polycationic hydrolyzing polyester amidamines gives substances which are used as precipitants or flocculants for biotechnological separation processes, for wastewater treatment and for the cationization of materials. formula

Description

be used.

3. The method according to claim 1 and 2, characterized in that the starting materials in the ratio of proton-bearing condensable amino and hydroxy groups to carboxylic acid and / or carboxylic acid ester groups of 0.8: 1 to 1: 0.8, preferably 1: 1 at Condensation temperatures up to 290 ⁰ C, preferably up to 260 ⁰ C, condensed under exclusion of oxygen and at reduced pressure to co- and 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 are used as starting materials or their hydrolysis in water-soluble compounds.

5. The method according to claim 1 to 4, characterized in that the Polyesteramidamine be dissolved in water with equivalent amounts of acid per amino group.

6. The method according to claim 1 to 5, characterized in that the Polyesteramidamine be converted by known methods to corresponding ammonium salts.

7. The method according to claim 1 to 6, characterized in that present in the Polyesteramidaminverbindungen 0.1 % to 99% ester bonds, preferably 1% to 30%, based on the sum of ester and amide bonds.

Field of application of the invention

The invention relates to a process for the preparation of hydrolyzing polycationic compounds, which are used as flocculants in a wide range of economics, but especially for biotechnology. but are also suitable for clarifying wastewater and in papermaking as well as components for membrane and Symplexbildung. These compounds can be used wherever Ηοί / amidamine is currently used.

Characteristic of the known state of the 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 substances are permanent, hydrolytically difficult to decompose, polycationic polymers that accumulate 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 well-suited to bio-protein flocculation, 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 a retention center! et al 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 hydrolyze easily to barely or non-toxic substances.

Explanation of the essence of the invention

The invention is based on the object, by using more suitable starting materials, a new class of polycations

create.

According to the invention the object is achieved in that sul-substituted di- or polyamines and / or substituted aminoalkylhydroxy compounds and / or substituted Alk> 'hydroxyaminocarboxylic acids and / or dicarboxylic acids and / or substituted Aminomono- or aminodicarboxylic acids and / or the ester derivatives of the corresponding carboxylic acids and / or (Meth) acrylic acid ester according to known transesterification and / or condensation process to Polyesteramidaminen with

the general formula

"θ - (NX)" ~ CO } - _t J-JiY ~ (NZ)

"Ff ⁰⁰ TtT

- o ^J /: o ^L / γ *> -o -V- ο

-fo - (NX-) ~ θ] --- - (- CO- * (NX ") ^C

^u LiO "'(= 0 or 1 ^u

- 0

- Γ - - (NZ ') ^ NY' J-CO j- if-

^L i I 0 Λ = 0 or 1 ^L 7 = O or Λ \} j £ £

be implemented. It is advantageous, as starting components compounds of the general formula

/ < ^CH 2> a _v Ί - ^(CH 2 ⁾ a _v

- _χ N- (CH ₂ ) JN ^ _/ NR ₂

(CH ₂ ) _b ^ ¹ _d

and or

^J f

and or

CH ₂ = C-CO-OR ₈

R ₇ and / or

R ₉ -O-CO-R ₁₀ -CO-OR ₉ and / or

HO-CH-COOR ₁₂ Rn

and / or R _n -CO-OR ₁₄

Ri, R _2, Ra, RI7 · -H; hydroxyalkyl; -CH ₂ -CH-COOR ₈

R ₇

R ₄₁ R ₆ ... alkyl; Allyl; -Cx-NR, R _6, e

-Cx-phenyl; -Cx-aryl hydroxyalkyl; -CHHpH-COORe

R7 R ₆ ... -H; Hydroxyalkyl; -CH ₂ -CH-COOF ₁₈ ;

R7

^R 4 f -H; Alkyl; -Cx-CN R ₇ , Ru ... -Cx-phenyl; -Cx-aryl -Cx COOR ₈ -H; alkyl; allyl R ₈ , Rs, Ri ₂ . ·· -Cx-phenyl; -Cx-O-CO-C-CH ₂ R7 hydroxyalkyl; -Cx-NRi ₅ Ri ₇ alkylene; phenylene; arylene Rio ··· Halogen; oxyalkyl; oxyphenyl; oxyalkylenephenyl Ru alkyl; phenyl; alkylenephenyl Rh ... Alkyl; -Cx-phenyl R i6, RiS ··· -Cx-O-CO-C = CH _2; Hydroxyalkyl ρ "7 0.2 to 4, if a = O then b Φ O from... O to 5 c, d, e, f ... Alkylene with χ CH ₂ units Cx ...

use.

The starting materials are in the ratio of proton-bearing, condensable amino and hydroxy groups to carboxylic acid and / or carboxylic ester groups from 0.8: 1 to 1: 0.8, preferably 1: 1 at condensation temperatures up to 29O ⁰ C, preferably up to 260 ° C. , Condensed with exclusion of oxygen and at reduced pressure to co- and terpolymers with a defined degree of branching and eliminated as a solid product. An embodiment of the invention provides that the starting materials or their hydrolysis products are soluble in water. Hydrolyzing "linear" clyceramateramines are obtained when bifunctional-condensable compounds are preferably used for synthesis The resulting, preferably non-polymeric, polycationic polyalkyleneamide compounds possess polycationic properties and are indefinitely storable with the exclusion of water but must be inferior prior to use Solubility can be brought into solution with the addition of up to equimolar amounts of acid per amino group in water, but the corresponding ammonium salt compounds can also be prepared from the products prepared by methods known per se, stored and dissolved in aqueous media without further addition hydrolyze the Polyesteramidamine under autocatalytic hydrolysis of Estersollbruchstellen at a defined rate in little or non-toxic, water-soluble substances depending on the structure According to the variation of the composition of ester amine and amidine amine components, the rates of hydrolysis of the polycondensates can be adjusted by the concentration of defined breaking points. The polycondensates 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 the charge density distribution of crucial importance for Polycation effect are.

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

EXAMPLES General rule for Kunuensaiion before, Pclyocterarriidaminen:

0.5 primer carboxylic acid and / or carboxylic acid ester groups in the basic substances used are used with exactly (0.5 Grundmol-x) proton-bearing amino groups substituted basic substances and χ Grundmol hydroxy-substituted basic substances in substance and under exclusion of oxygen with purging with inert gas (argon, nitrogen) and possible addition of transesterification catalysts slowly heated to 18O ⁰ C. The resulting volatile product is abdesiiiiicii. After completion of Vüf condensation, the temperature is reduced under reduced pressure

After condensation to a maximum of 290 ⁰ C increased until no volatile product is produced. After cooling, the linear or branched product, depending on the composition and degree of condensation, is present as a tough or solid polymer mass which, depending on the composition, optionally with the addition of acid, dissolves in water to an equimolar amount. By well-known methods, the Polyesteramidamine can also be converted into the slightly water-soluble, quaternary Polyasteramidammonium compounds

 Following the above rule, the following products were co-condensed with conventional polyamidoamine components:

- Polyamideamine component:

(A) piperazine

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

H-N-i

CHI.

CH ₂ - CH ₂ .N - + H

CIL

Λ 1 i η ί 5 Ν, Ν'-diallylethylenediamine and derived derivatives of the structure

-7

H ₀ - CHo - N 4- H

R-N-I

Cn ₂

CH ₂ = CH

with R

R '

-H;

-J-CH.

CH ₂ - N -4- H

R '

O £ η - 5

R '... alkyl; allyl

Methyl (meth) acrylate (meth) acrylic acid ethylstyrene (meth-1-acyl acrylate N'-methyl- or N'-allyl-dipropylenetriamine

Co-component to form polyesteramidamine:

(0) Ethyl chloroformate and / or diethyl carbonate

(1) (meth) acrylic acid ^ -hydroxyethyl ester

(II) Di (meth) acrylic acid glycol ester (glycol di (meth) acrylate]

(III) N-methyl-N- (2-hydroxyethyl) -β-amino propanoate and / or (2-hydroxyethyl) ester

(IV) N-Allyl-N- (2-hydroxyethyl) -β-amino-propanoic acid methyl ester and / or 3-chloro (2-hydroxyethyl) ester

(V) N-methyl-N- (2-hydroxyethyl) amino-ethanoic acid methyl ester

(VI) a-hydroxyethanoic acid methyl ester

(VII) 1,4-dioxane-2,5-dione

(VIII) a-Hydroxypropanoic acid ethyl ester

(IX) N-methyl and / or N-allyl-N, N-dipropanoic acid (2-hydroxyethyl ester) amine

(X) N-methyl and / or N-allyl diethanolamine

(XI) N, N'-di (2-hydroxyethyl) piperazine

(XII) N-methyl and / or N-allylethanolamine

(XIII) N- (2-hydroxyethyl) piperazine

(XIV) Terephthalic acid di (2-hydroxyethyl) ester [diglycol terephthalate]

- Cocomponents to be used as branching substance:

(XV) ethanolamine

(XVI) diethanolamine (XVII) triethanolamine (XVIII) triethanolamine triacrylate ester triethanolamine triacrylate]

(XIX) diethylenetriamine and / or dipropylenetriamine

(XX) amino-di- (propanoic acid methyl ester)

(XXI) Amino-di (propanoic acid 2-hydroxyethyl ester)

(XXII) N, N, N ', N'-tetra- (propanoic acid methyl ester) -ethylenedi, min

(XXIII) N, N, N ', N'-tetra (propanoic acid 2-hydroxyethyl ester) ethylenediamine

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 is carried out with cleavage of the main chain in fragments that have less or no toxic effect and further biodegrade too little or non-toxic compounds.

Claims (2)

1. A process for the preparation of polyester amidamines, characterized in that substituted di- or polyamines and / or substituted aminoalkylhydroxy Verbindi ngo.n and / or substituted Alkylhydroxyaminocarbonsäuren and / or dicarboxylic acids and / or substituted aminomono- or dicarboxylic acids and / or ester derivatives of corresponding carboxylic acids and / or (meth) acrylic acid ester according to known transesterification and / or condensation process to polyester amidamines of the general formula 0 - (NX) <~ CO) -NY r * (NZ) ^ COt- *> 0 jliO L ftlO 'Yr-O 0 ^ (NX ») ^ Of / -CO ^ (NX") ^ CO HO -Ie = O or 1 ^L. ^ IO - # = or ¹ " ^l " NY 'r>(NZ')"" * NY 'fCO j- 12 0 V = O or 1 ^k '1 = 0 ^ = 0 or be implemented. 2. The method according to claim 1, characterized in that as starting component compounds of the general formula R _{1 In} ^ ^a \ n - (ch ₂ ) _c -I-N _n a ₂ L (CHq), ^J J ^ "9'V ₁ d and / or Lp "~ -P P R ₄ f R ₅ CH ₂ = C-CO-OR ₈ R ₇
and or R ₉ O-CO-R ₁₀ -CO-OR ₉ and or HO-CH-COOR ₁₂ Rn and or R ^ ₃ -CO-OR ₁₄ R ·., R2, R3, Ri7 · -H; hydroxyalkyl, -CH ₂ -CH-COOR ₈ R ₇ R ₄ , R ₅ ... alkyl; allyl; -Cx-N R ₁₅ R ₁₆ -Cx-phenyl; -Cx-aryl-CH ₂ -CH-COOR ₈ ; hydroxyalkyl R ₇ -H; Hydroxyalkyl; -CH ₂ -CH-COOR ₈ ; R ₇ ) - N
e ι ^R 4 " R ₇ , Rii ... -H; Alkyl; -Cx-CN -Cx-phenyl; -Cx-aryl -Cx COOR ₈
Re, R9, Ri2 ··· -H; Alkyl, allyl -Cx-phenyl; -Cx-O-CO-C = CH ₂ R ₇ hydroxyalkyl; -Cx-NR ₁₅ R ₁₇
R ₁ O- alkylene; phenylene; arylene R ₁ S ... halogen; oxyalkyl; oxyphenyl; oxyalkylenephenyl R ₁₄ ... alkyl; phenyl; alkylenephenyl Ri ₅ , R ₁₆ ... -alkyl; -Cx-phenyl -Cx-O-CO-C = CH _2; hydroxyalkyl R ₇ a, b ... · 0.2 to 4; if a = O, then b = £ O c, d, e, f ... O to 5 Cx ... alkylene withxCH ₂ units