CS241790B1 - Process for preparing 3-thiapentyloxy derivatives of polyphosphazene - Google Patents

Abstract

The method for preparing poly(3-thiapentyloxyphosphazenes) consists in a polymer-analogous substitution reaction of poly(diochlorophosphazene) with 3-thiapentyl oxide and an alkali metal fluoroalkoxide, carried out in a mixture of anhydrous solvents at room temperature in an inert atmosphere in a single-step or multi-step process. The 3-thiapentyloxydervates of polyphosphazene serve as intermediates in the preparation of the corresponding sulfinyl derivatives as polymer analogues of dimethyl sulfoxide.

Description

The invention relates to a process for the preparation of 3-thiapentyloxy- and fluoroalkoxy-substituted polyphosphazenes.

Copolymers of styrene-divinylbenzene with attached sulfide moieties are known as intermediates for further functional conversions to form polymeric reagents and catalysts (Coli. Czech. Chem. Commun. 4, 1818 (1982), Polym. Bull. 11, 215 (1984)). ).

A disadvantage of poly (styrene-co-divinylbenzene) -based polymers is the inertness of the crosslinked skeleton from the point of view of the catalytic effect, and also the method of matrix functionalization in terms of synthesis. Its first step is the chloromethylation of styrene-divinylbenzene copolymers with highly carcinogenic chloromethyl methyl ether. Subsequent refunctionalization of chloromethylated copolymers to form polymers involving sulfide groupings | it does not often go into high degrees of transformation.

The essence of the process for preparing the 3-thiapentyloxy derivatives of polyphosphazene according to the invention consists in reacting alkali metal 3-thiapentyloxide and fluoroalcohol alkoxide RCFgCHgOH, where R = F, CHFg, with poly (di-chlorophosphazene) in anhydrous solvent mixture tolulen-tetrahydrofuran up to 2 and 1, at room temperature in an inert atmosphere by a one-stage or multi-stage process.

The reaction of the invention results in soluble copolymers in which the 3-thiapentyloxy and fluoroalkoxy groups are arranged both statistically and in blocks, and their structure is summarized in detail (4-p = N). - (P = Ν) - (- P = Nfcr

Λ AA ^(I)

R ^ R ^ 2. Rg Rg Rg where R ₊ = OCHgCHgSCgH4, Rg = OCHgCFgR and R = F, CHFg.

The structure of the copolymer depends on the order in which the components are reacted. In the preparation of static copolyphosphazenes, the poles (dichlorophosphazene) are reacted with a mixture of alkali alkoxides of 3-thia-1-pentanol and fluoroalcohol RCF CH OH, where R = FjCHFg, and in the preparation of block copolyphosphazenes, such that. the polyols (dichlorophosphazene) are reacted sequentially and subsequently with fluoroalcohol alkoxides RCF-CH3OH, where R = F, CHFg, and 3-thia-1-pentanol in a mixture of anhydrous toluene-tetrahydrofuran solvents.

The reaction can be carried out practically with quantitative refunctionalization of the starting poly (dichlorophosphazene) to give products in which the molar ratio R R / (R ^ + Rt) is between 1% -93%.

The advantage of the process according to the invention is the high reactivity of the starting poly (dichlorophosphazene) enabling the preparation of polymers with a high degree of furificationization. The polymer backbone together with the substituents resulting from the subsequent modification of sulfide structures are prerequisites for participation in catalytic action in organic reactions and complexing with ions of metals.

The following examples illustrate the invention without limiting it.

Example 1

To a 20 ml solution of 20 mmol sodium 3-thiapentyloxide and 20 mmol 2,2,3,3, -tetrafluoropropoxide in anhydrous tetrahydrofuran was added dropwise 26.9 ml of a solution of pole (dichlorophosphazene) in toluene (c = 28.6 g) with stirring. 1; ~ dl / g) at room temperature. The reaction mixture was allowed to stand for 4 hours and the product was isolated by precipitation into hexane and purified by reprecipitation from acetone to water. The product contains 47 wt. 3-thiapentyl oxy substituents; unreacted chlorine content 0.05 wt.

Example 2

To 15 ml of a 1 M solution of sodium 3-thiapentyloxide in anhydrous tetrahydrofuran was added dropwise with stirring over 60 min. at poko241790

- 3 ml of 14.5 ml of a solution of poly (dichlorophosphazene) in toluene (c = 20.3 g / l; gj = 3 * 25 dl / g). The mixture is allowed to stand for 3 Families and then 7.5 ml of a 2M solution of sodium 2,2,3,3-tetrafluoropropoxide in anhydrous tetrahydrofuran is added in one portion. The mixture was stirred for 19 hours and the product was isolated by precipitation into ethanol. The product contains 92 wt. 3-thiapentyloxysubstituents} unreacted chlorine content 0.21 wt.

Example 3

To 5 ml of a 1M solution of sodium 2,2,3,3, -tetrafluoropropoxide in anhydrous tetrahydrofuran is added dropwise 34 ml of a solution of poly (dichlorophosphazene) in toluene (c = 17> 1 β / 1 25 25 ⁼ 1 ^{dl dl} / ®) ^with stirring at room temperature. The reaction mixture was allowed to stand for 2 hours and then 10 ml of 1M sodium 3-thiapentyloxide in anhydrous tetrahydrofuran was added portionwise with stirring. After standing for 2 hours, 15 mmol of 2,2,3,3-3-tetrafluoropropoxide in 15 ml of anhydrous tetrahydrofuran are finally added in one portion and the product is isolated by precipitation in hexane after 3 hours and purified by precipitation from acetone *.

into water. The product contains 40 wt. 3-thiapentyloxy substituents arranged in blocks; unreacted chlorine content <0.01 wt.

Claims (4)

OBJECT OF THE INVENTION A process for the preparation of 3-thiapentyloxy derivatives of polyphosphazene characterized in that the poles (dichlorophosphazene) are reacted with the alkali alkoxides of 3-thia-1-pentanol and fluoroalcohol RCF-CH 2 OH, wherein R = F, CHF _2> in a mixture of anhydrous solvents tolulene-tetrahydrofuran in a ratio of 1 to 2: 1 by volume, at room temperature in an inert atmosphere in a one-stage or multi-stage process. 2. Process for the preparation of static copolyphosphazenes according to claim 1, characterized in that the poly (dichlorophosphazene) is reacted with a mixture of alkali alkoxides of 3-thia-Rpentanol and a fluoroalcohol 'RCFgCHgOH' where R = F, CHF ₂ . 3. A process for preparing block kopolyfosfazenů ^ according to claim 1 wherein the poly (dichXorfos'fazen) was reacted sequentially with alkoxides fluoroalkoholu RCF ₂ CH ₂ OH where R = F, CHF _2, and 3-thia-1-pentanol in given order. AND 4. A process for the preparation of poly (alkoxyphosphazenes) according to (1), characterized in that the poly (dichlorophosphazene) is reacted sequentially with alkoxides of 3-thia-1-pentanol and fluoroalcohol RCFgCHgOH, where R = F, CHF ₂ , respectively.