CS241789B1 - Process for preparing oligo (oxyethylene) polyphosphazene derivatives - Google Patents

Abstract

The method of preparing oligo(oxyethylene) derivatives of polyphosphazene consists in reacting poly(dichlorophosphazene) with alkaline alkoxides with the structure of oligo(oxyethylenes) having 1-10 oxyethylene units in a mixture of anhydrous solvents toluene-tetrahydrofuran in a volume ratio of 1 to 2 : 1 in the presence of alkaline alcoholates of fluoroalcohols RCP2CH2OH, where R is F, CHF2, at room temperature. The advantage of the method of preparing polymers is the high reactivity of the starting poly(dichlorophosphazene) and the nature of the products of its modification, in which, when used as catalysts, the catalytic effect of the introduced groups is enhanced by the participation of the main chain. Crown ether and pseudocrown ether derivatives of polyphosphazene are used as catalysts of organic reactions and for capturing metal cations from solutions.

Description

(54)

Process for preparing oligo (oxyethylene) derivatives of polyphosphazene

A process for the preparation of oligo (oxo ethylene) polyphosphazene derivatives is to react poly (dichlorophosphazene) with alkali alkoxides having the structure of oligo (oxyethylenes) having 1-10 oxyethylene units in a mixture of anhydrous solvents tolulene-tetra-drofuran. 1: 2: 1 v / v in the presence of alkali alkoxides of fluoroalcohols RCP 2 CH 2 OH, where R ss F, CHF 2, at room temperature.

The advantages of the process for the preparation of polymers are the high reactivity of the starting poly (dichlorophosphazene) and the nature of its modification products, in which, when used as catalysts, the catalytic effect of the introduced groups is enhanced by the participation of the main chain. Crownether and pseudocrownether polyphosphazene derivatives are used as catalysts for organic reacols and for trapping metal cations from solutions ·

241,789 (11) B, (51) Int. CIA

OJ C 08 G 79/02

The invention relates to a process for the preparation of oligo (exyethylene) polyphosphazene derivatives.

Oxygen (oxyethylenes) are used as suitable reaction media as well as efficient catalysts for a number of organic substitution, elimination and hydrolytic reactions.

Oligo (oxyethylenes) have previously been coupled to an insoluble polymer backbone, styrene-divinylbenzene copolymers (J. Amer. Chem. Soc. 101.4249 (1979), J. Org. Chem. 48,195 (1983), Synth. Commun. 13,443 (1983) and have been commercially available (ALDRICH) in recent years, in addition to their catalytic action in similar reactions to oligo (oxyethylenes), complexing properties have been shown to be a disadvantage of these crosslinked oligo (oxyethylene) copolymers. lower catalytic efficiency per unit weight of catalyst than for the oligo (oxyethylenes) themselves, based on chloromethylated styrene-divinylbenzene copolymers, which are produced using highly carcinogenic methyl-chromethylether;

SUMMARY OF THE INVENTION The present invention provides a process for the preparation of polyphosphazene oligo (oxyethylene) derivatives, characterized in that poly (dichlorophosphazene) is reacted with alkali alkoxides having an oligo (oxyethylene) structure having 1-10 oxyethylene units in a mixture of anhydrous tolulene-tetrahydrofuran solvents in volume. a ratio of 1 to 2 µl in the presence of alkali fluoroalcohols RCFgCHgOE, where R = F, CHFg, at room temperature.

The oligo (oxyethylene) used contain 1 - 10% oxyethylene units. To ensure the replacement of all chlorine (and thus the hydrolysis of the products), the reactions are carried out in the presence of the alkali alkoxides of the fluoroalklb RCF (CH3 OH), where R = F, CHFg.

By the process of the invention polymers having different hydroxyl group contents can be prepared, wherein from the alkoxyalkoxide form of the olifloether reagents _; containing 1-10 oxyethylene units, polymers with a higher hydroxyl group content are formed, and from the dialkoxide form of the oligoether reagents containing 1-10 oxyethylene units, low hydroxyl group polymers.

By the reaction of the invention, the oligo (oxyethylenes) bind to the poly (phosphazene) chain via one or two oxygen bridges in one or two substitution centers intra- and intermolecularly to form crosslinked polymers with controllable oligo (oxyethylene) groupings, some of which form cells or segments with a pseudocrownet structure.

An advantage of the process according to the invention is the very nature of the starting pole (dichlorophosphazene) as a highly reactive monotopically di-substituted polymer which allows

- formation of pseudocrownether structures,

- wide-ranging introduction of oligo (oxyethylene) clusters, degrees of refunction,

- formation of hydrolytically stable cross-linked and soluble copolymers with controllable content of hydrophobic fluoroalkoxy substituents, and thus synthesis of a polymer whose backbone itself, together with the introduced substituents, has the prerequisites for catalytic action and complexing. metal cations from solutions.

Example 1

To 20 ml of a 0.5 M solution of disodium 3,6,9,12-tetraoxatetradecamethylene-1,14-dioxide in anhydrous tetrahydrofuran was added 0.93 ml (10 mmol) of 2,2,3,3-tetrafluoro-1- To a homogeneous solution of the alcoholates is added dropwise 38.8 ml of a solution of poly (dichlorophosphazene) in anhydrous toluene over 90 minutes with vigorous stirring.

17.1 g / L; [%] = 2.77 dl / g) and the mixture was further stirred for 3 hours. The swollen polymer is separated, washed with hexane, acetone and water. Pro241789

3 product contains 45% of the theoretically possible amount of oligoether side chains and 1.1 mmol / g of free OH groups; unreacted chlorine content 0.26 wt.

Example 2

O

To a mixture of 20 ml of a 0.5 M solution of disodium-36,9,12,15,18-hexaoxaeicosamethylene-1,2-dioxide in anhydrous tetrahydrofuran and 20 ml of a 0.5 M solution of sodium-2,2,3,3-tetrafluoropropoxide in anhydrous tetrahydrofuran, dropwise over 90 minutes, 39 ml of a di-group (dichlorophosene) in anhydrous toluene (n = -17.1-g / l; J 25 ⁼

2.77 dl / g). The reaction mixture was allowed to stand for 3 hours, after which the swollen polymer was separated, washed with hexane, acetone and water. The product contains 67% of the theoretically possible amount of hepta (oxyethylene) side chains and 0.9 mmoVg of free hydroxyl groups; % unreacted chlorine content 0.15 wt.

Example 3

To 15.6 ml of a 2.5 M solution of 3,6-dioxa-1,8-octanediol in anhydrous tetrahydrofuran was added 15 mg equiv. sodium and after dissolution of 10 ml of a 1.5 M solution of sodium 2,2,3,3-tetrafluoropropoxide in anhydrous tetrahydrofuran. To the mixture was added dropwise 38 ml of a solution of poly (dichlorophosphazene) in anhydrous toluene (c = 17.1 g / l; 25 25 "-2 77 77 'dl / g) over 90 minutes at room temperature and the mixture was allowed to stand for 3 minutes. clock. The swollen polymer is separated, washed with hexane, acetone and water. The product contains 40% of the maximum possible content of tri (oxyethylene) side chains and 1.7 mml / g of free hydroxyl groups; content of unreacted chlorine 0.82% by weight

Example 4

To a mixture of 6.8 ml of a 0.5 M solution of sodium 3,6,9,12,15,18-hexaoxacyclooctadecyl methoxide in anhydrous tetrahydrofuran and 15 ml

- 4 no

A 0.5 M solution of sodium 2,2,3,3-tetrafluoropoxide in anhydrous tetrahydrofuran is added dropwise with stirring over 60 minutes with a solution of 37.5 ml of a solution of poly (dichlorophosphazene) in anhydrous toluene (e - 17.1 g / lf fj25 = 2.77 dl / g) at room temperature. The reaction mixture was allowed to stand for 3 hours. The product was isolated by precipitation into hexane and purified from acetone solution into water. The product contains 10% of the theoretical maximum amount of 18-crown-6-units; unreacted chlorine content <0.01 wt.

Claims (4)

SUBJECT OF THE INVENTION A process for the preparation of poly (phosphorylated) aligo (oxyethylene) derivatives, characterized in that the poles (dichlorophosphazene) are reacted with alkali alkoxides having an oligo (oxyethylene) structure having 1-10 oxyethylene units in a mixture of anhydrous, tolulene-tetrahydrofuran solvents in a volume ratio 1 to 2: 1 in the presence of alkali fluoroalcohol alcohols RCFgCHgOH, where R = F, CHFg, at room temperature. 2. A process for the preparation of higher hydroxyl group oligo (oxyethylene) derivatives of polyphosphazene according to claim 1, characterized in that the poles (dichlorophosphazene) are reacted with alkoxyalkoxides having an oligo (oxyethylene) structure having 1-10 oxyethylene units. 3. A process for the preparation of lower hydroxyl group oligo (oxyethylene) derivatives of polyphosphazene according to claim 1, characterized in that the poly (dichlorophosphazene) is reacted with dialkoxides having an oligo (oxyethylene) structure having 1-10 oxyethylene units. 4. A process of preparing polyphosphazenes with bonded cyclic unit according to claim 1, wherein the alkoxide hydroxymethylcrownetheru fluoroalcohol and RCF ^ H ^ OH wherein R and F, CHF _2> reacting 3 poly (dichlorfosfazenem) single-stage or multistage. Corrections in printed descriptions of the invention In the printed description of the invention for the author's certificate No. 241 789, the year of the invention application was incorrectly printed.