NO145976B - APPLICATION OF ETHERS OF POLYHYDROXYMYL METHOD AS IONE EXCHANGERS - Google Patents

Description

The invention relates to the use of ethers of polyhydroxymethylene as ion exchangers.

As a substitute for starch and gelatin in adhesives and binders or as emulsifiers, cellulose derivatives, among other things, have been used in chemical engineering for a long time. Moreover, the biochemical technique in particular requires - in recent years increasingly - for chromatographic separation methods in addition to adsorption materials of a general type, especially ion exchangers, for e.g. to obtain amino acid or protein fractions from the present mixtures. It is known to meet these requirements, e.g. to use cellulose ethers. In order to generally etherify cellulose, this is reacted in an alkaline medium in an inhomogeneous phase with alkylating agents, e.g. with halogenated fatty acids. If the cellulose ethers are to be used as ion exchangers, etherification agents with substituents that have ionic groups are used for their production. Preferably, with these preferences, the primary hydroxyl groups of the anhydroglucose unit are attacked, first, secondarily, the secondary hydroxyl groups.

The disadvantage of cellulose ethers and thus also the ion exchangers produced from them lies in the fact that they are labile to chemical and enzymatic attacks, a property that stands against their wide application in techniques for biochemists, physiologists and medics.

The task of the invention is to avoid this disadvantage.

This is successful, as ethers of polyhydroxymethylene are used as ion exchangers. The object of the invention is consequently the use of ethers of polyhydroxymethylene with ionic or ionizable substituents from the group of carboxyl, sulfo, phospho, quaternary ammonium or substituted amino residues as ion exchangers. The polyhydroxymethylene used as starting material in the method according to the invention is a known polymer, the production of which e.g. is discussed by H.C. Haas and N.W. Schools

in J. Polym. Science, 31, 238 (1958).

It was surprisingly found that polyhydroxymethylene, although it has exclusively secondary hydroxyl groups, is available for a substitution to ethers. In the method for producing the ethers, the reaction is preferably carried out according to the following two methods: 1. Mixing the components polyhydroxymethylene, isopropanol and NaOH solution in the mixer and adding the alkylating agent at approx. 50-90°C, preferably at approx. 70°C. 2. Dissolving the polyhydroxymethylene in an approx. 20-50% by weight NaOH solution at room temperature and addition of the alkylating agent at approx. 20-90°C, preferably approx. 70-90°c.

These reactions can therefore be carried out in an aqueous-alkaline medium in a heterogeneous phase, possibly with the addition of an organic solvent such as isopropanol which dilutes,

and - a significant advance due to the more even possibility of substitution, e.g. against conditions for the production of cellulose ethers - also in homogeneous phase. Polyhydroxymethylene is insoluble in the aqueous solvents such as water, alcohols, esters, acetone, dimethylformamide, ethers, benzene, toluene, chloroform, dimethylsulphoxide and is only slightly swollen by them in some cases: it does, however, dissolve in alkaline solutions, such as e.g. in 25-50% by weight NaOH solutions already at room temperature, at

about. 80°C, a 20% by weight NaOH solution is already sufficient for this purpose.

When diluting the solutions or other reduction

of the NaOH concentration, with progressive etherification according to method 2, part of the polyhydroxymethylene may again precipitate out, however, if a solubility of the formed ether in water is given, then the reaction can also be continued in a homogeneous phase.

The alkylating agent to be used must, due to the ion exchange properties to be achieved, next to one or more groups suitable for ether formation at least have a functional group that is ionic or ionizable, this includes a carboxyl, sulfo, phospho, quaternary ammonium or substituted amino residue. Substances such as the following are suitable for this task: N,N-dialkylamino-g-chloroalkanes

N,N-diarylamino-3-chloroalkanes

3-chloro-2-hydroxypropyl-trimethylammonium hydrochloride 2,3-epoxypropyl-trimethylammonium hydrochloride ethyleneimine

chloroacetic acid

dichloroacetic acid

trichloroacetic acid

^-chloroethanesulfonic acid

vinyl sulfonic acid

chloroethane phosphoric acid

vinyl sulfonic acid

chloroethanephosphonic acid

vinylphosphonic acid

N,N-dichloro-ethyl-alkylamines

N,N-dichloro-ethyl-arylamines

The products obtained according to the invention can be water-soluble or largely water-insoluble. Influencing these latter properties is possible by choosing substituents, by the degree of substitution or by network formation with at least bifunctional reagents.

An advantage achieved with the invention lies in the fact that the substances used according to the invention are of higher chemical resistance, so that they are not easily degraded. In particular, they also resist enzymatic and other biochemical degradation processes. Their ion exchange ability with ionic or crypto-ionic substances e.g. under biochemical and physiological-chemical conditions is excellent, which is why they can find wide application possibilities as ion exchangers in biochemistry, medicine and physiological chemistry.

In the following examples, the stated percentages mean weight percentages and MS means molar degree of substitution.

Example_el_l

An amount of 50 g of polyhydroxymethylene (1.67 mol, referred to the basic building block of the polymer) was mixed in a bucket with 250 ml of 87% isopropanol and 66.8 g of the 50% aqueous NaOH solution (0.84 mol ) within 30 minutes at 25°C. The etherification took place by dropwise addition of 168 g of a 50% aqueous solution of 3-chloro-2-hydroxypropyl-trimethylammonium hydrochloride (0.45 mol) and subsequent heating to 70°C for 60 minutes. The reaction mixture was then diluted with methanol and neutralized against phenolphthalein with glacial acetic acid. The white powder formed after filtration was washed with aqueous methanol and dried at 60°C. It contained 0.5% N, which corresponds to a MS of approx. 0.01.

Example_el_2_

An amount of 15 g of polyhydroxymethylene (0.5 mol) was introduced into 120 g of a 24% aqueous NaOH solution (0.7 mol) in a 500 ml three-necked flask, heated to 70°C and stirred for 45 minutes at this temperature. The etherification took place by dropping 188 g of a 50% aqueous solution of 3-chloro-2-hydroxypropyl-trimethylammonium hydrochloride into the viscous, gel-like solution over 10 minutes. The solution thereby lost viscosity and part of the substance fell out. The reaction mixture was poured into 500 ml of water, filtered, washed with water, isopropyl alcohol and acetone, dried at 60°C and then ground. The white powder thus formed contained 1.8% N, which corresponds to an MS of 0.05.

Example_3

An amount of 10 g of polyhydroxymethylene (0.33 mol) was dissolved in 75 g of a 40% aqueous NaOH solution (0.75 mol) and stirred for 45 minutes at 70°C. The etherification took place by adding 65 g of glycidyl-trimethyl-ammonium chloride (0.43 mol) and subsequent heating and stirring at 70°C for 45 minutes. The reaction mixture was poured into 500 ml of water, filtered, washed neutral with water, dried at 60°C and then ground. The water-insoluble powder formed after the dialysis in aqueous suspension against water and a subsequent freeze-drying contained 1.0% N, which corresponds to an MS of 0.02.

Example_4

The procedure was as in example 3, but 100 g of 2-chloroethane-sulfonic acid Na salt (0.6 mol) was used as etherification agent. The water-insoluble powder contained 3.0% S, which corresponds to a DS (degree of substitution) of 0.03.

Example_el_5

The procedure was as in example 3, but with 58 g of 2-chloro-ethyl-diethylamine (0.43 mol) as etherification agent. The water-insoluble powder contained 4.3% N, which corresponds to a DS of 0.13.

Example_el_6

A quantity of 15 g of polyhydroxymethylene (0.5 mol) was dissolved in caustic soda, which contained 44 g of NaOH (1.1 mol) in 200 g of water and the viscous mass was heated for 45 minutes at 80-90°C. The etherification took place by dropwise addition of 59 g of an 80% aqueous monochloroacetic acid solution (0.5 mol) and subsequent heating to 80-90°C over the course of one hour. After cooling and neutralization with glacial acetic acid against phenolphthalein, it was diluted with water to 500 ml and precipitated by infusing for approx. 4 liters of methanol. The white powder formed after filtration was washed three times with pure methanol, after which the powder was free of chlorides. It was then dried at 60°C and pulverized in a mortar. Yield 17.6 g. The water-soluble product contained 8.85% Na, which corresponds to a DS of 0.175.

Example_7

The procedure was as in example 3, but with 84 g of dichloroacetic acid (0.66 mol) as etherification agent. The water-insoluble powder contained 1.5% Na.

Example_8

The procedure was as in example 3, but with 35 g of trichloroacetic acid (0.22 mol) as etherification agent. The water-insoluble powder contained 3.1% Na.

Claims (1)

Use of ethers of polyhydroxymethylene with ionic or ionizable substituents from the group of carboxyl, sulfo, phospho, quaternary ammonium or substituted amino residues as ion exchangers.