CS260552B1 - Process for the preparation of (2-oxo-1-pyrrolidinylmethyl) derivatives of styrene polymers and copolymers - Google Patents

Abstract

The subject of the solution is a method for producing (2-oxo-1-pyrrolidinylmethyl) derivatives of styrene polymers and copolymers, consisting in the fact that a chloromethylated polymer or copolymer of styrene reacts under interphase transfer conditions with 2-pyrrolidone in the presence of an alkali hydroxide and a quaternary ammonium salt, which catalyzes the interphase transfer.

Description

The present invention relates to a process for the preparation of (2-oxo-1-pyrrolidinylmethyl) styrene polymer derivatives and copolymers.

(2-oxo-1-pyrrolidinylmethyl) derivatives of styrene polymers and copolymers of formula (I)

CH ₂

CH ₂ -N ₂ ^X CH ₂ -CH is an immobilized form of the known dipolar aprotic solvent N-methylpyrrolidone. N-methylpyrrolidone, poly (n-vinylpyrrolidone) and (2-oxo-1-pyrrolidinylmethyl) polystyrene derivatives and styrene copolymers greatly accelerate nucleophilic substitution reactions. This catalytic activity is of particular interest in insoluble crosslinked derivatives which are readily removed from the reaction mixture by filtration and which can be reused.

(2-oxo-1-pyrrolidinylmethyl) styrene polymers and copolymers can be prepared by reacting styrene polymers and copolymers with N- (hydroxymethyl) pyrrolidone in the presence of acid catalysts such as trifluoroacetic acid. AO 260 467. A disadvantage of this production process is the need for the preparation of N- (hydroxymethyl) pyrrolidone in a special step, and in particular the use of relatively expensive and corrosive catalysts.

The present invention provides a process for the preparation of (2-oxo-1-pyrrolidinylmethyl) styrene polymer copolymers by reacting a halomethylated polymer and a copolymer with 2-pyrrolidone in the presence of an alkali hydroxide and a quaternary ammonium salt which interphase transfer catalyses.

Among the alkali hydroxides, sodium hydroxide and potassium hydroxide are suitable.

The reaction proceeds according to the following scheme. The chloromethylated polymer or styrene copolymer of formula II is reacted with the 2-pyrrolidone of formula III in the presence of an alkali hydroxide of MOH, where M = Na, K and quaternary ammonium salts under interfacial transfer catalysis (PTC) conditions with CH-Cty ^+. ch ₂ ci (II) ch ₂ —ch ₂ ch ₂ co \ /

NM (III)

CH-CH ₂ '

MOH

PTC

CH ₂ CO — CH,

M = Na, K ch ₂ —ch ₂ (I)

The reaction is preferably carried out in a two-liquid system - an organic and an aqueous or a solid-liquid system. The organic phase consisting of chlorinated or aromatic hydrocarbons serves as the medium for the polymeric chloromethyl derivative which is either dissolved or swollen therein. The aqueous phase then contains pyrrolidone and an alkali hydroxide. However, it is also possible to work in an anhydrous environment where all the reactants except the pyrrolidone are solid. Interfacial transfer catalysts, quaternary ammonium salts, always mediate the interactions of the reaction components in different phases.

As quaternary ammonium salts, benzyltriethylammonium chloride, tetrabutylammonium bromide, methyltrialkylammonium chloride with C8- ^C10 alkyls are preferably used. It is based on readily available polystyrene chloromethyl derivatives which are common industrially manufactured intermediates for the manufacture of anion exchangers. The products can be obtained by a one-step synthesis. Interfacial transfer catalysts are used only in small amounts and can be reused. Finally, the chemicals used in the present invention are neither toxic nor corrosive.

(2-oxo-1-pyrrolidinylmethyl) derivatives of polymers and copolymers of styrene are very efficient polymeric interfacial transfer catalysts which can be used in various reactions of organic substances with an inorganic reactant, eg alkylation of inorganic and organic salts to form esters, ethers, thiocyanates , nitriles and other products.

He did

A mixture of 0,5 g of chloromethylated styrene-2% divinylbenzene copolymer (Cl content 19,8%) swollen in 10 ml of toluene, 0,5 g of 2-pyrrolidone, 1,5 ml of 50% sodium hydroxide and 0,25 g of methyltrialkylammonium chloride ( alkyls C _g to C _lo, Adogen 464, Ashland Chemical Co.) was heated with stirring at 100 ° C for 100 hours. The polymer was then filtered off and washed with water and methanol. Product characteristics: nitrogen content 2.04% i.e. 1.46 mmol pyrrolidone groups / g; strongly absorbs in the infrared range at 1,690 om ^-1 .

Example 2

At the same weight and procedure as in Example. 1, with the only difference that instead of a mixture methyltrialkylamoniumchloridů (alkyl C _g to C _g Adogen 464, Ashland Chemical Co.) was used benzyltriethylammonium chloride, 0.58 g of the product of the N content is 2.00%.

Example 3

With a mixture of 0.5 g of the copolymer of Example 1 swollen in toluene (15 ml), 0.5 g of pyrrolidone, 0.7 g of finely divided sodium hydroxide, 1.4 g of finely divided potassium carbonate (KgCOg) and 0.15 g of the mixture methyltrialkylamoniumchloridů (alkyl C _g to C _g Adogen 464, Ashland Chemical Co.) was hydroformylated in the same manner as in example 1 was obtained 0.66 g of product containing 1.99% nitrogen.

He attaches

With a mixture of 0,5 g of chloromethylated styrene-divinylbenzene copolymer (Amberlite XE 305, Rohm & Haas) containing 12.5% Cl, 0.5 g of 2-pyrrolidone, 1.5 ml of 50% sodium hydroxide (NaOH),

0.25 g of triethylbenzylammonium chloride was carried out in the same manner as in Example 1. Yield of the product 0.69 g, nitrogen content 1.68%.

Example 5

With a mixture of 0,5 g of chloromethylated styrene-2% divinylbenzene copolymer (Cl content 16,9%),

0.5 g of 2-pyrrolidone, 2 ml of 50% sodium hydroxide (NaOH) and 0.25 g of a mixture methyltrialkylamoniumchloridů (alkyl C _g to C _g Adogen 464, Ashland Chemical Co.) was hydroformylated in the same manner as in Example 1. It was 0.61 g of product with a nitrogen content of 1.62% was obtained.

Claims (2)

EXAMPLE, EDMET OF THE INVENTION A process for the preparation of (2-oxo-1-pyrrolidinylmethyl) styrene polymer copolymers and derivatives, characterized in that the chloromethylated polymer or styrene copolymer is reacted under 2-phase transfer conditions with 2-pyrrolidone in the presence of an alkali hydroxide and a quaternary ammonium salt. 2. A process according to claim 1, wherein the alkali hydroxide is sodium or potassium hydroxide.