SU365365A1 - METHOD FOR OBTAINING POLYMERS WITH LUMINESCES - Google Patents

Description

one

The invention relates to the field of producing polymers containing luminescent groups, which are necessary for studying the relaxation properties and conformational transformations of polymers in the solid state, melt or solution by luminescent methods.

A known method of producing luminescent anthracene-containing nolymers by the polymerization of anthrylmethyl esters of acrylic acids or their copolymerization with other monomers in the presence of radical initiators.

The proposed method differs from the known one in that vinyl-9-anthrylmethyl ether or its mixtures with other vinyl ethers are used as initial monomers. The polymerization process is initiated by cationic tin catalysts.

This difference makes it possible to obtain polymers with different contents of luminescent anthracene groups.

Polymerization of vinyl-9-anthrylmethyl ester. And copolymerization with ethers of the formula X-CH CH-O-Alk, where, Alk, OAlk, in ampoules, in an atmosphere of dry argon, using shnritsevoy technology. The catalyst VRZO (SOI5) 2, the solvent is dry toluene.

The polymers obtained are purified by repeated reprecipitation followed by washing of the Koii precipitator, repeating this operation until the number of anthracene groups in the samples ceases to change. The polymers obtained in this way, purified from low molecular weight anthracene containing impurities, contain covalently attached anthracene groups, as shown by UV spectroscopy, fluorescence, and polarized luminescence.

Example 1: Homopolymerization of vinyl-9 anthryl methyl ether.

0.3 g of vinyl-9-anthrylmethyl ether is dissolved in 8 ml of toluene. With cooling to -78 ° C, 0.1 ml of a solution of VrzO (C2H5) 2 in toluene (m-ol / l) is introduced. The polymerization is carried out for 4 days, at 78 ° C. The polymer is planted in a tenfold excess of methanol. After drying under vacuum, 0.24 g of light yellow polymer is obtained (yield 80%). i in toluene at 20 ° С 0.05. The UV spectrum of the polymer contains absorption bands characteristic of monosubstituted 9-alkyl anthracene. The IR spectrum confirms the presence of a simple ether link in the polymer.

Example 2- Copolymerization of vinyl-9-anthri l methyl and vinyl benzyl esters.

51 mg (0.215 mmol) of vinyl-9-anthrylmethyl ether and 2 ml (14.3 mmol, previously distilled over sodium and then over ZiAin vinylsulfonate, dissolved in 6 ml of toluene. With cooling at -78 ° C

0.6 ml of a solution of a catalyst in toluene (from 2 mol / l) is introduced into the solution. Copolymerisation is carried out for 20 hours. at -78 ° C. The polymer is planted in methanol. After drying in vacuo, 1.74 g of a yellowish polymer is obtained (yield 87%). The polymer, purified by pycrates, re-precipitated from solution in toluene to methanol, contains an anthracene group of 135 vinyl benzyl ether units. g in benzene at 20 ° C 0.25.

Example 3. Copolymesis. And vinyl-9-anthrylmethyl and pro-propyl-benzyl refluxes.

10 mg (0.04 mmol) of vnpl-9-anthrylmethyl ether and 3 ml (20 mmol) are pre-purified by repeated distillation over sodium of propenyl benzyl ether, dissolved in 6.3 ml of toluene. When cooled to -78 ° C, 0.67 ml of a solution of catalysts in toluene (from 0.5 mol / l) is introduced into ipacTBop. Polimerisations are carried out for 19 hours at about 78 ° C. Polymer is dissolved in methanol. After drying in vacuo, 0.37 g of a white polymer is obtained. The polymer, och; ish, which is five times re-precipitated from a solution in chloroform to methanol, contains one anthracene group on 1,900 propenyl benzyl ester t | in toluene at 20 ° С 0.34.

Example 4. Copolymerization of vipil-9-apt) ylmethyl ether and 1,2-dimstoxyethylep .5.34 g of vinyl-9-a1grylmethyl ester (C, C, 6 ml of 1,2-dimethoxyethylia) is dissolved in 6 ml of toluene. When cooled to -78 ° C, 0.02 ml of boron trifluoride etherate is added with stirring. The copolymerization is carried out for 20 hours at -78 ° C. The copolymerization is stopped by the addition of methanol and the resulting

the polymer is planted in petroleum ether. The polymer yield 0.36 g (40%). The copolymer, purified 5 times by re-precipitating from serium ether to petroleum ether, contains one anthracene group of 1150 units.

poly: -1,2-methylmethoxyethylene. c in chloroform at 20 ° C 0,2.

Subject invention

The method of obtaining polymers with luminescent groups by polymerization and copolymerization of the corresponding monomers, characterized in that, in order to expand the range of luminescent polymers, vinyl-9-anthrylmethyl ester or mixtures thereof are used as initial monomers. other vinyl esters, and the polymerization process is carried out in the presence of cationic catalysts.