FI61495B - FREQUENCY REARING FOR SUSPENSION OF A POLYHYDROXIMETHYLENE - Google Patents

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Federal Republic of Germany Förbundsrepubliken Tyskland (DE) P 25U0688.6-month (71) Hoechst Aktiengesellschaft, 6230 Frankfurt / Main 80, Federal Republic of Germany Förbundsrepubliken Tyskland (DE) (72) Michael Kostrzewa, Wiesbaden, Karl-Frieden , Germany Li i tt ot asavalta-Förbundsrepubliken lyskland (DE) (7U) Oy Kolster Ab (5U) Method for the preparation of polyhydroxymethylene ethers for use as ion exchangers

The invention relates to a process for the preparation of polyhydroxymethylene ethers for use as ion exchangers from polyhydroxymethylene and an alkylating agent in an alkaline aqueous medium, optionally with the addition of an organic solvent.

It has long been used in chemical technology as a substitute for starch and gelatin in adhesives and binders or as emulsions, e.g. cellulose derivatives. In addition to this, the technique of biochemistry in particular has in recent years increasingly required special ion exchangers for chromatographic separation methods in addition to general adsorption materials, e.g. for amino acid or protein separation from mixtures. To meet these needs, the use of cellulose ethers, for example, is known. The etherification of cellulose is generally carried out by reacting it in an alkaline dye in an inhomogeneous phase with alkylating agents, e.g. halogenated fatty acids. When cellulose ethers are to be used as ion exchangers, etherifying agents with ion group-containing substituents are used. In such etherification, the primary hydroxyl groups of the 2,61495 anhydroglucose units react primarily and only secondarily with the secondary hydroxyl groups.

The disadvantage of cellulose ethers and the ion exchangers made from them is that they are unstable against chemical and enzymatic effects, a property which hinders their widespread use in biochemical, physiological and medical technology.

The object of the invention is to eliminate this disadvantage.

This object is achieved by preparing polyhydroxymethylene ethers by a process in which various alkylating agents can be used. The products prepared by the method are suitable for use as ion exchangers. This process is characterized in that the alkylating agent containing quaternary ammonium or substituted amino groups is reacted with polyhydroxymethylene at 20-90 ° C.

The polyhydroxymethylene used as a starting material in the process according to the invention is a known polymer, the preparation of which has been described e.g. by H.C. Hass and N.W. Schuler, J. Polym. Science, 31, (1958), 238.

Surprisingly, it was found that although polyhydroxymethylene has only secondary hydroxyl groups, it can be converted to an ether via substitution. The process according to the invention preferably uses the following two processes: 1. The components, polyhydroxymethylene, isopropanol and NaOH solution, are mixed in a kneading machine, and an alkylating agent is added thereto at about 50-90 ° C, preferably at about 70 ° C.

2. The polyhydroxymethylene is dissolved in about 20-50% by weight NaOH solution at room temperature, and an alkylating agent is added thereto at about 20-90 ° C, preferably at about 70-90 ° C.

Thus, these reactions can be carried out in an alkaline-aqueous medium as a heterogeneous phase, optionally using an organic solvent such as isopropanol as an additional diluent, and as a substantial step forward, e.g. Polyhydroxymethylene is insoluble in common solvents such as water, alcohols, esters, acetone, dimethylforamide, ethers, benzenes, toluene, chloroform, dimethyl sulfoxide, and only some of these swell slightly. However, it is soluble in temporal solutions, such as, for example, 257-30 'of 3,61495% by weight NaOH solution already at room temperature, and at 80 ° C a solution of 20% by weight of NaOH is sufficient for dissolution.

By diluting the solutions or otherwise reducing the NaOH content of the solutions, some of the polyhydroxymethylene may reprecipitate in Method 2 as the etherification continues. However, if the ether formed is water-soluble, the reaction can also continue as a homogeneous phase.

In order to achieve ion exchange properties, the alkylating agent used must contain at least one functional, ionic or ionizable group, such as a quaternary ammonium or substituted amino group, in addition to one or more groups forming an ether formation. Suitable compounds are: N, N-dialkylamino / 3-chloroalkanes N, N-diarylamino / S-chloroalkanes 3-chloro-2-hydroxypropyltrimethylammonium hydrochloride 2,3-epoxypropyltrimethylammonium hydrochloride ethyleneimine N, N-dichloroethylalkyl -dikloorietyyliaryyliamiinit.

The products prepared according to the invention may be water-soluble or largely insoluble in water. The latter property can be influenced by the choice of substituents, the degree of substitution and crosslinking with at least bifunctional reagents.

One advantage of the invention is that the products obtained with it have an increased chemical stability, so that they are not automatically cleaved. They are also persistent, especially with respect to enzymatic and other biochemical degradation processes. When they contain ionic or ionizable groups, their ion exchange capacity with respect to ionic or cryptoionic substances, e.g. under biochemical and physiological-chemical conditions, is excellent.

The polyhydroxymethylene ethers according to the invention can therefore be widely used, e.g. as ion exchangers in biochemistry, medicine and physiological chemistry.

The percentages given in the following examples refer to weight percentages and MS denotes a molar degree of substitution.

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Example 1 50 g of polyhydroxymethylene (1.67 moles based on polymer base units) were mixed in a kneader with 87% isopropanol (250 ml) and 50% aqueous NaOH (66.8 g, 0.84 mol) for 30 minutes. ° C. The etherification was carried out by dropwise addition of 168 g of a 50% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium hydrochloride (0.45 mol) and then heating at 70 ° C for 60 minutes. The reaction mixture was then diluted with methanol and neutralized with glacial acetic acid using phenolthalein as an indicator. The resulting white powder was filtered and washed with aqueous methanol and dried at 60 ° C. It contained 0.4% N, corresponding to about 0.01 MS.

Example 2 15 g of polyhydroxymethylene (0.5 mol) in 120 g of 24% aqueous NaOH solution (0.7 mol) were introduced into a 500 ml three-necked flask, the mixture was heated to 70 ° C and stirred at this temperature for 45 minutes. The etherification was effected by dropwise addition of 188 g of a 50% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium hydrochloride to a viscous, yellowish solution over 10 minutes. The viscosity of the solution then decreased and some of the material precipitated. 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 obtained contained 1.8% N, corresponding to 0.05 MS weather.

Example 3 10 g of polyhydroxymethylene (0.33 mol) were dissolved in 75 g of 40% aqueous NaOH solution (0.75 mol) and the solution was stirred for 45 minutes at 70 ° C. The etherification was carried out by adding 65 g of glycidyltrimethylammonium chloride (0.43 mol) and then heating and stirring at 70 ° C for 45 minutes. The reaction mixture was poured into 500 ml of water, the precipitate was filtered off, washed with water until neutral, dried at 60 ° C and ground. The water-insoluble powder obtained by dialysis against water and subsequent freeze-drying in an aqueous suspension contained 1.0% N, corresponding to 0.02 MS.

Example 4

The procedure was the same as in Example 3, but using 58 g of 2-chloroethyldiethylamine (0.43 mol) as the esterifying agent. The resulting water-insoluble powder contained 4.3% N, corresponding to 0.13 DS.

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Comparative Examples In accordance with R. C. Schulz's article "ttber die Sulfoalkyllierung von Polymethylol" (Die Makromolekulare Chernie, 133 (1970), 307-309), the following reactions were performed:

Comparative Example 1 2 g of polyvinylene carbonate in 100 ml of 2.5 N NaOH solution were reacted with 45 g of propane sultone for 5 hours.

About 10% of the polymethylol ether remained insoluble. The sulfur content of the insoluble matter was low, about 1%. The rest of the polymethyl ether was water soluble and could not precipitate upon addition of 10 times the amount of methanol to the aqueous solution. Based on the parameter values reported by Schulz, the MS value of the water-soluble part can be calculated to be about 0.05.

Comparative Example 2 2 g of polyvinylene carbonate in 10 ml of 2.5 N NaOH solution were reacted with 70 g of propane sultone for 6 hours.

About 10% of the polymethylol ether remained insoluble; its sulfur content was low. The rest of the polymethol ether was water soluble and could be precipitated by adding methanol to the aqueous solution. The sulfur content of the precipitated product was about 6.1%, which corresponds to an MS value of about 0.07.

The polymethylol ether prepared by the process of the invention using 3-chloro-2-hydroxypropyltrimethylammonium hydrochloride (see Example 2) having the same MS value of 0.05 as the blood of the product prepared in Beauty Example 1 was completely insoluble in water and thus suitable for use as an ion exchanger.