DE2262284A1 - Polyetheramines - useful as flocculating agents, dewatering agents, antistatics etc - Google Patents

Abstract

Water sol. high mol. polyetheramines (A) and salts of these are made by (1) reacting excess of an aliphatic polyamine (B) contg. >=1 primary or 2 sec. amino gps., and opt. OH gps., with a mol. wt. of is not >200, with a polyhaloether (C) contg. units of formula: where hal = Cl or Br, n=1, 2 or 3, and m = whole number, and the product of n and m = 5-30, (2) distilling off excess (B), (3) cross-linking the resulting polyetheramine (D) in aqs. soln. until the viscosity rises and opt (4) reacting part of all the free amino gps. with an acid to form the corresponding salt.

Description

Dipl.-Ing. P. WIRTH Dr. V. SCHMIED-KOWARZIK DIpl.-lng. G. DANNENBERG Dr. RWElNHOLD Dr. D. GUDEL

TELEPHONE «, β ,,, β FRANKFURT AM MAI« '

287014 GR. ESCHENHEIMER STHASSE 38

SANDOZ AG

Basel (Switzerland) Case 1.50-3351

Method of manufacture

from new polyether amines and their uses

The invention relates to a process for the preparation of water-soluble, high molecular weight polyether amines (A) and their salts with acids by reacting aliphatic polyamines (B) ₉ containing at least one primary or two secondary amino groups and optionally hydroxyl groups whose molecular weight is at most 200, in excess With polyhaloethers »removal of the excess polyamines from the reaction mixture by distillation and crosslinking of the polyether amine (D) obtained in this way in aqueous solution Ms, an increase in viscosity occurs, whereupon the free amino groups may be wholly or partially due to the addition of acids

Salts are transferred according to patent (registration) P 21 27 082.6, which is characterized in that a compound (C) is used as the polyhaloether, the units of the general formula

in which shark
η

CH,

CH -CH ₂ shark

CH,

I ^c

CH,

n-1

C,

2 shark

Chlorine or bromine 1, 2 or 3 and an integer being the product

m times η are 5 to 30, preferably 7 to 20, contain.

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The polyhaloether (C) in question can ζ., B. manufactured by, in a known manner, a compound of the formula (E)

ClCH ₂ CH ₂

(E)

where η and Hai have the meaning given above, in Polymerized in the presence of a Lewis acid.

The polyamines in question and the implementation conditions the various reactions (the conversion between polyamine and polyhaloether and the subsequent crosslinking) are the same as those described in the main patent (registration) are.

The compounds of formula (E) can be prepared in a known manner (e.g. according to the process described in E.P. 7 ^ 9 713) getting produced.

In their production from 2-haloethanol and epichlorohydrin Mixtures of products of the formula (E) can arise in which η 1.2 or 3 * depending on the proportions of the starting products. These mixtures can are polymerized as such to give compounds of the formula (C),

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or their components can first be isolated and then polymerized will.

The excess of starting amines necessary to avoid the formation of excessively crosslinked and thus insoluble reaction products depends on the product m χ n, the reactive polyhaloether to be converted (C): the latter is of high molecular weight (many reactive residues), a larger excess must be used than with low molecular weight polyhaloethers (less reactive Groups). The necessary excess of starting polyamine is considerable, at least 2-3 moles of polyamine, based on a reactive group in the polyhaloether, must be used.

The reaction can according to the invention advantageously between 50 - 150 ⁰ C are performed.

Practically all reactive groups are expediently made to react. This point is reached when nearly the theoretical Amount of halogen ions in the reaction mixture can be detected.

Another object of the present invention relates to the end products obtained by the process described above and their use as a flocculant and flotation agent for the treatment of wastewater from cities and industrial plants, and antistatic agents for textiles, hers is surprising high activity as a drainage agent and retention aid in the Paper industry.

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In the above description and in the following examples, which illustrate but not limit the invention, mean parts by weight.

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example 1

A mixture of 60 parts methylene chloride, 14 parts of 2-Chloräthylglycidyläther and 1.7 parts of 30% aqueous fluoroboric acid solution is heated with stirring to about 40 ⁰ C. A clear solution emerges after a short time. After removing the heating bath, 71 parts of 2-chloroethylglycidyl ether are added dropwise to the solution in such a way that a gentle reflux is maintained. The solution is then stirred for a further 2 hours at 40-45 ° C. After removal of the methylene chloride, 86 parts of a brown, viscous product are obtained as residue which corresponds to the reactive polyether of the formula (C) (n = 1, Hai = Cl). The average molecular weight (vaporometric determination of the molecular weight according to Chylewski and Simon, HeIv. Chim. Acta 47.515 1964) was 1124.

86 parts of the polymer thus produced are dissolved in 338 parts of diethylenetriamine. The solution is heated to 135 ° C. and stirred for a further 3 hours at this temperature. After cooling the reaction mixture to about 80 ° C., 83 parts of 30% strength aqueous NaOH solution are added. Then water and excess diethylenetriamine are distilled off in vacuo. After heating to 110-150 ⁰ C at 20-10 torr with stirring to constant weight 159 parts residue is obtained, consisting of 36.5 parts of sodium chloride and 122.5 parts Polyätheramin.

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To 31 parts of the above residue, dissolved in 4-9 parts 25 parts of a 30% strength aqueous solution are added to water of the bis-chlorohydrin of the formula

Cl Cl®

φ φ

Cl-OH ₂ -CH-CH ₂ - ^ - € H ₂ -CH-CH ₂ -N-CH ₂ -CH ₂ -Cl-KJH OH CH ₅ CH ₃ OH CH ₅ ^- CH ₅ OH

to and the thin liquid mixture left to react for 18 hours at 65 ⁰ C. A viscous solution is obtained which contains JO% active ingredient and which can be diluted with water to form a homogeneous solution.

Example 2

.Effect on the drainage of paper stock The measure of "drainage" is the time it takes for the Exit of a certain amount of filtrate from a one according to the invention Dewatering agent-containing suspension of a certain paper stock composition is required in Compared to that obtained from a corresponding amount of filtrate from a suspension containing a known dehydrating agent needed. The test method used is in the leaflet V / 7/61 of the "Association of Pulp and Paper Chemists and Engineers ". The results obtained clearly show the superiority of the dehydrating agent obtained according to the invention.

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Claims (5)

Claims I. Process for the preparation of water-soluble, high molecular weight polyether amines (A) and their salts by reacting aliphatic polyamines (B) ₁ containing at least one primary or two secondary amino groups and optionally hydroxyl groups whose molecular weight is at most 200, in excess with polyhaloethers, removal of the excess polyamine (B) from the Beaktionsgemisch by distillation, and crosslinking the thus obtained Polyätheramins (D) occur in aqueous solution to an increase in viscosity, after which optionally the free amino groups are completely or partially converted by addition of acids into their salts (according to Patent application ) P 21 27 082.6, characterized in that a compound (C) is used as the polyhaloether, the units of the general formula CH -CH ₂ shark CH
CH, CH, I ' CH, n-1 Shark 309827/1037 where shark is chlorine or bromine
η 1, 2 or 3 tmd m is an integer where the product m times η 5 to 30 »preferably 7 to 20, contain. 2. "The method according to claim 1, characterized in that the reaction between polyamine (B) and the reactive polyhaloethers (C) at a temperature between 50 ° and 150 ⁰ C is carried out. 3. The Po Iy ät her amine (A) prepared according to claim Γ became. 4-. Use of the polyether amines prepared according to claim 1 (A) as flocculation, flotation, dewatering and Retention aids or as antistatic agents. 5. Paper, the obtained according to claim 1 in the production thereof Polyether amine (A) were used as an aid. The patent attorney 309827/1037