DD268594A3 - METHOD FOR PRODUCING HYDROLYZING POLYCATION COMPOUNDS - Google Patents

Abstract

The invention relates to a process for the preparation of polyesteramines or polyesteramidamines in which polycondensation of low molecular weight compounds of the general formula HO (NX) a0ZHROOC & (NY) b0CO! ORg0 or 1 with Z ... 0, NR hydrolyzing polycationic polyesteramines or polyesteramidamines are obtained p H range 7 swell or dissolve in water. The aim of the invention is to develop a new and at the same time simple process for the preparation of polycationic, hydrolyzing polyesteramines which have significance as precipitants and flocculants for biotechnological separation processes, for wastewater treatment and for the cationization of materials.

Description

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 especially for biotechnologies, but also for the clarification of wastewater and in papermaking and as components for membrane or Symplexbildung.

Characteristic of the bekannton technical solutions

It is known to use polyamideamines, substituted poly- and copolyacrylic esters, poly- and copolyacrylamide compounds, 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, polyketionic polymers that accumulate over time in nature and are usually fischoxic fishisch when they are used in flours for flocculation and so get into the water. Although they are very well suited to the bio-protein flocculation, they lead to disturbances in the gastrointestinal tract when feeding the flaked bio-protein to animals. According to CH-PS 606133, pendent-type polycations are used as retention agents and the like. 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 which decompose hydrolytically in the aqueous medium after use, d. H. lose their Polykationwirkung and easily hydrolyze to barely or non-toxic substances.

Explanation of the essence of the invention

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

According to the invention the object is achieved in that dicarboxylic acids and / or substituted aminodicarboxylic acids and / or their ester derivatives with alkylenediols and / or substituted amino-alkylhydroxy compounds of the general formula

HO - (NX) _λ > ₀ ~ ZH + ROOC JMNY) ^> ₀ ~ ^C ° H - 0 or 1 with Z ... 0, NR *

be reacted according to known Umestorungs- and / or condensation process to polyester or polyester amines. Advantageously ht, the compounds

H i 0

-CH- CHU A _u - B. - A _J 4 CH - CH - θ! - Η

R <

2 "2" 1

with the connections

RO-CO- (RJ X CH - CH - A - B. - Λ, - CH - Ch | - COOR, ^{3 4} f T ^ι I ^{δ h} * I ι Jk: ³ »

_ R ₅ ^R 6 ^Λ 6

w at A

... 4H- (GHo) ₁ f _m ( ^N ) ~ n

L R R_

R ₇ Λν ₈

^ VWIl ₀ JII / (CH ₀ ) VI

B ... 4N _n ^ά °> Ν - (CH ₂ ) JLN _n ^ά ° Nf

¹ (CH ₂ ) ^{ά q} ^ _r L ( ^CH 2) p "^

R ₁₁ R ₂ ... -H; alkyl; hydroxyalkyl

R ₃ ... -H; alkyl; hydroxyalkyl; phenyl

R _{4 is} -alkylene, phenylene; arylene

R ₆ , R ₆ ... -H; alkyl; C _x -CN; -C _x -COOR ₃

R ₇ , R ₈ ... -Ci-C ₄ -Alkyl; allyl; hydroxyalkyl; -C _x -COOR ₃ ; -C _x -phenyl; -C _x -aryl; -C _x NR ₉ R ₁₀

R ₉ , R ₁₀ ... -alkyl; allyl; C _x -phenyl; -C _x -aryl; -C _x -CN

a ... 1 to 5

b, c, d, g, h, i, n, s ... OodeM

e, l, m, q, r, χ ... Ο to 5

f, k ... OodeMmitf ^ k

o, p ... 0,2bis4, ifo = 0dannp ^ 0

C _x ... AlkylenmitxCH ₂ units and / or

R ₁₁ O - C - R ₁₂ O

Rn ... alkyl, phenyl, alkylenephenyl

R ₁₂ ... halides, oxyalkyl, oxyphenyl, oxyalkylenephenyl

mean to implement.

The starting materials are used in the ratio of proton-bearing amino and / or hydroxyl groups of from 1.8: 1 to 1: 0.8, preferably from 1: 1 to condensation temperatures of up to 29O ⁰ C, preferably to 26O ⁰ C, under oxygen aussc iluß and condensed at reduced pressure to homo-, co- or 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.

There are obtained hydrolyzing, linear or branched polyester amines or polyester amidamines which are formed from preferably amino or Polyaminodi- or -polycarboxylaten and amino or Polyaminomono- to -polyhydroxy compounds. The resulting, preferably uncrosslinked, polycondensate products can be stored indefinitely in substance with the exclusion of water, but must be brought into solution before use with equivalent amounts of acid in water. However, the corresponding ammonium salts can also be prepared from the products prepared by processes known per se, stored and dissolved in aqueous media without further additions.

embodiments

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

0.1 basic carboxyl ester or carboxylate groups of the amino or polyamino compound are in the ratio 0.8: 1 to 1.2: 1, preferably in equimolar amounts of moles with proton-bearing amino and / or di- and / or Polyhydroxyl-substituted, tertiary amino or polyamino compounds, in a reaction vessel with exclusion of oxygen and rinsing with inert gas (argon, nitrogen) and optionally with the addition of transesterification catalysts slowly heated to 22O ⁰ C and distilling off the resulting volatile product. After completion of the precondensation, the temperature is increased to the postcondensation to preferably 26O ⁰ C under reduced pressure. The condensation reaction is over when no volatile product is produced. After cooling, the linear, branched or crosslinked product, depending on the homo-, co- or terpolymer and degree of condensation, is in the form of a tough, rubbery or solid polymer mass which dissolves in water with the addition of equimolar amounts of acid per amino group. ill of strongly branched or crosslinked polyesteramines or polyesteramidamines with or without hydrophobic Kettense onte only swells.

By generally known methods, the tertiary amine compounds can be converted into and used as the readily soluble or swellable quaternary ammonium compounds.

According to the above mentioned instruction, the following products were used for homo-, co- and terpolycondensation in the ratio COOR: OH (NHR) = 1: 1:

(O) ethyl chloroformate and / or diethyl carborane

- dicarboxylates oxalate (D Malonsäutediethylester (II) adipate (III) dimethyl terephthalate (IV) ß, P'-Oxydipropansäurediethylester (V)

Tertiary amino or polyaminedicarboxylates

(VI) N-methyl. "=> Mino-diethanoic acid ethyl ester

(VII) N-allylamino-diethanoic acid ethyl ester

(VIII) N-methylamino-ß, ß'-diprone acid methyl ester

(IX) N-Allylamino-ß.p'-dipropanoic acid methyl ester

(X) N-Methyiamino-β, β'-di- (α-methylpropanoic acid methyl ester)

(XI) N-Allylamino-β, β'-di- (α-methylpropanoic acid methyl ester)

(XII) N, N'-dimethyl-N, N'-diethanoic acid ethyl ester ethylenediamine

(XIII) N. N'-diallyi-N, N'-diethanoic acid ethyl ester ethylenediamine

(XIV) N, N-dimethyl-N, N'-.beta.-bis-dipropanoic acid methyl ester ethylenediamine

(XV) N, N'-Diallyl-N, N'-β, -dipropanoic acid, methyl ester diamine

(XVI) N, N-dimethyl-N, N'-.beta., .Beta.-di- (α-methylpropanoic acid methyl ester) ethylenediamine

(XVII) N, N'-diallyl-N, N'-.beta.-.beta.-di- (α-methylpropanoic acid, hylester) ethylenediamine (XVIII) .sub.2, .beta.-Oiethansäureethylester-piperazine

(XIX) Ν, Ν'-β, β-dipropanoic acid methyl ester piperazine

(XX) N, N'-.beta., .Beta.-Di- (a-methylpropanoic acid methyl ester) piperazine

(XXI) N, N ', N "trimethyl (N, N" -diethanoic acid, ethyl ester, diothylene triamine

(XXII) N, N ', N "-trimethyl-N, N" -β, β-dipropanoic acid methyl ester diethylenetriamine

(XXIII) N, N ', N "-trimethyl: N, N" -β, β-di- (α-methylpropanoate) diethylenetriamine

(XXIV) N, N "-dimethyl-N'-allyl-N, N" -diethanoic acid ethyl ester diethylenetriamine

(XXV) N, N "-dimethyl-N'-allyl-N, N" -dipropanoic acid methyl ester diethylenetriamine

(XXVI) N, N "-dimethyl-N'-allyl-N, N" -di- (α-methylpropanoic acid, methyl ester) diethylenetriamine

(XXVII) N, N-dimethyl-N'-N'-diethanoic acid ethyl ester n-propylenediamine

(XXVIII) N, N, N'-N'-N, N'-N-β-bis-dipropanoate, n-propylenediamine

(XXIX) N, N-dimethyl-N ', N'-.beta., .Beta.-di- (α-methylenepropanoic acid methyl ester) n-prepylendiamine

Tertiary amino or polyamino compounds which have two or more carboxyl groups and hydroxyalkyl groups and can crosslink in the condensation reaction or serve as branching or crosslinking substances:

(XXX) Aminotriethanoic acid ethyl ester

(XXXI) aminotri-ß, ß, ß-propanoic acid methyl ester

(XXXII) Ν, Ν, Ν ', Ν'-ethylenediamine tetraethanoic acid ethyl ester

(XXXIII) Ν, Ν, Ν ', Ν'-β, β, β, β-tetrapropanoic acid methyl ester ethylenediamine

(XXXIV) N- (2-hydroxyethyl) amino-diethanoic acid ethyl ester

(XXXV) N- (2-Hydroxymethyl) -amino-N, N-.beta., .Beta.-dipropanoic acid methyl ester

(XXXVI) N- (2-hydroxyethyl) amino-N, N-β, β-di- (α-methylpropanoic acid methyl ester)

(XXXVII) N '- (2-hydroxyethyl) -N, N "-dimethyl-N, N" -diethanoic acid ethyl ester diethylenetriamine

(XXXVIII) N '- (2-hydroxyethyl) -N, N "-dimethyl-N, N" -β, β-dipropanoic acid methyl ester diethylenetriamine (XXXIX) N' - (2-hydroxyethyl) -N, N "-dimethyl- N, N -beta ", ß-di- (a-methylpropansäureniethylester) -diethylenetriamine

Glycols, amino or polyamino-dihydroxy compounds;

Amino- or polyaminopolyhydroxy compounds as branching or crosslinking substance:

(A) Ethylene glycol

(B) propylene glycol-1,2 or propylene glycol-1,3

(C) ethanolamine

(D) N-methyldiethanolamine

(E) N-allyl diethanolamine

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

(G) N- (2-hydroxyethyl) piperazine

(H) N, N-di (2-hydroxyethyl) -N ', N'-dimethyl-n-propylenediamine.

- Branching and crosslinking agents (I) triethanolamine

(K) N, N, N ', N'-tetra (2-hydroxyethyl) ethylenediamine

(L) diethanolamine-N-ethanoic acid ethyl

(M) Diethanolamine N-.beta.-propanoic acid hemyl ester

(N) diethanolamine-N-β- (α-methyl-propanoic acid methyl ester)

Linear polyesteramines or polyesteramidamines are used in the homo-, co- and terpoiycondensation of the dicarboxylate compounds (I) to (XXIX) with the bifunctional compounds (A) to (H) old. These polycondensates dissolve with the addition of äqu ^! Molar quantities of acid in water on bw can easily be converted to the quaternary water-soluble ammonium compound by well-known methods. Depending on the desired degree of branching or crosslinking, the substances (XXX) to (XXXIX) or (I) to (N) can be added in appropriate amounts for homo-, co- and terpoiycondensation. The branching or crosslinking substances (XXX) to (XXXIX) and (A) to (N) or (I) to (XXXIX) and (I) to (N) in the homo-, co- and terpoiykondensation highly branched ProJukte. In the case of the compounds (VI) to (XXIX), instead of the methyl and ethyl esters, the 2-hydroxyethyl esters were used which condensed directly by heating under vacuum distillation of the resulting ethylene glycol to the polyesteramine compound without addition of another di- or polyhydroxy compound. The compounds (XXX) to (XXXIX) behave analogously as 2-hydroxyethyl esters, except that branched or crosslinked products are formed here.

The resulting main chain polyesteramide condensates hydrolyzed under defined conditions in the aqueous medium easily with statistical cleavage of the main chain in water-soluble, low or non-toxic products with loss of Polykationenwirkung. The hydrolysis rate is pH-dependent. In the neutral range, the condensates are degraded to non-toxic compounds within a few transmissions up to about 60 days, depending on the choice of substituents. 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 (5)

claims: 1. A process for the preparation of hydrolyzing polycationic compounds, characterized in that dicarboxylic acids and / or substituted aminodicarboxylic acids and / or their ester derivatives with Alkyiendiolen and / or substituted amino-alkylhydroxy compounds of the general formula HO (NX) ^ ₀ ^ ZH + ROOC [~ (NY) ^> _Q with Z ... 0, be reacted according to known transesterification and / or condensation process to polyester or polyester amines.
2. The method according to claim 1, characterized in that the compounds - CH - C - B - A _A f CH - CH
c α ι, ₍ - c | _e - H with the connections Ii, 0 -CO- (Rj ^{3 4} where A ·. « CH - CH - A - l Ι β ί; ' ¹ J " ¹ ' < ^0H 2> - A. - CH I
rc - ¹ A COOR mean to implement. Alkyl, phenyl, alkylenephenyl Halogen, oxyalkyl, oxyphenyl, oxyalkylenephenyl 3. The method according to claim 1 and 2, characterized in that the starting materials in the ratio of proton-bearing amino and / or hydroxyl to carboxyl groups of 0.8: 1 to 1: 0.8, preferably 1: 1 to condensation temperatures up to 290 ⁰ C, preferably at 260 ⁰ C, with exclusion of oxygen and condensed at reduced pressure 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 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 polyester amines or Polyesteramidamine be dissolved with equivalent amounts of acid in water. 6. The method according to claim 1 to 4, characterized in that the polyester amines or polyester amidamines are reacted by known methods to corresponding ammonium salts.