SU441812A1 - The method of obtaining polymers - Google Patents

Description

one

The invention relates to the preparation of polymers containing heterocycles in the chain. Such polymers have high heat resistance, and in a number of cases they have semi-annual properties.

A known method for the preparation of polymers is the reaction of b1isases of ides and bisacetylenes.

For the preparation of polymers having aziridine groups in the chain, according to the following: Ib proposes the iB method as unsaturated compounds that contain at least two unsaturated bonds.

The reaction is carried out by heating to 100-160 ° C.

In addition, the reaction is carried out under UV irradiation.

The process proceeds through an intermediate stage and can be represented by the following scheme.

/

  I

No

V

-with

prok / kutochny / nyoiJijKni

As can be seen from the above scheme, according to the proposed method, polymers are obtained that contain imie cycles in the main chain.

For polymer synthesis it is necessary that the functionality of each of the compounds used is at least two.

For the preparation of polymers can be used as compounds, simultaneously

containing both azido and unsaturated bonds

(i.p.mer, Ng-SbH4-C-OCHg-CH CH2),

ABOUT

and two compounds, one of which contains at least two azido groups, and the other at least two unsaturated bonds. As a last iMoryT, vinyl OR alkyl derivatives may be added. The reaction is carried out at elevated temperatures or by initiating with UV light at room temperature in the melt of monomers or in solution. As solvents can be used as compounds, dissolving monomers and polymers, and non-dissolving polymers or monomers. Iamen nature of monomers, can be in the widest limits to vary the chemical structure and properties

high molecular weight compounds obtained. For example, this method produces high molecular compounds containing only imine and aromatic cycles (used as starting compounds

diazide biphenyl and divinylbenzene)

 -. I

, or yuvoevoobraznye high-molecular compounds of structure II (when using as the original 15 compounds of bisazide biphenyl, and benzoquinone)

Along with the imine units in the chain, ester bonds may also be present.

GNSH 1

1- ABOUT STATE STD

(V -, - dJ in (11p, and using as the starting product allyl ester of azidobenzoic acid) The polymers obtained by the proposed method have high heat resistance. The results of thermogravimetric analysis are shown in the table.

2de B-

in the case of the preparation of isomolecular polyazirIdins And the moving terminal azido groups impart a high photosensitivity to polymer films, which makes it possible to use them as photoreistors in the photolithograph and on semiconductors.

The polymers have electrophotographic properties due to their high charging potential and sufficient photosensitivity.

PRI; AND MER 1. In the round bottom (equipolar flask, equimolar amounts of bisazide biphenyl and divinylbenzene are placed and heated slowly with stirring. At 100-160 ° C, vigorous evolution of nitrogen begins. 11p, and the temperature of the reaction mixture until the evolution of gas bubbles is complete (usually 1-4 hours). The product obtained is dissolved in dimethylformamide and aromatic hydrocarbons. Durable films can be cast from solutions in these solvents. Study of the IR spectra of the synthesized product, as well as elemental data analysis of the purified product, it is possible to propose formula I for it. t)

“Kf -) - CH, in dimethylformamide at 0.28 dl / g. The yield of purified product is 71%. Example 2. Equimolar amounts of bisazide biphenyl and divinylbeisol are placed in a round bottom flask with a broomstick, and then 200% by weight of the monomers of dimethylformamide are poured. With constant movement, the reaction system is heated to

140 ° C and kept at this temperature until the evolution of gas bubbles. As a result of the reaction, a polymer solution in dimethylformamide, colored in crown-brown color, rj in dimethylformamide and 20 ° C 0.12 dl / g is obtained. The yield of purified product is 63%.

Example 3. Equimolar amounts of bisazide biphenyl and benzoquinone are placed in a round bottom flask with a mixer, then 300% by weight of dimethylformamide monomer are added. After dissolving the monomers while simultaneously raising the temperature and stirring, the reaction mixture is kept at 110-160 ° C until complete

excretion of nitrogen, get a black polymer solution. The study of the IR spectra and the data of elemental analysis of purified by reprecipitation. In the chloroform of a limer, the formula P can be used for it. Polymer iB dimethylformamide can be cast.

.C1 CH III-CHiOH. The azido-benzoic acid alkyl ester is heated at 100-160 ° C until complete elimination of nitrogen is completed. Ex: and this get soluble in dimethylformamide nolymer with t 0.16 DL / g According to the IR spectra and elemental analysis, this LOL can be offered the formula P1. The yield of purified 10 product 82%. Example 5. Equimolar amounts of diviilbnzola and bisazide biphenyl are dissolved in a 5-fold (by weight of monomers) amount of benzene, placed in a quartz cuvette and irradiated at 20 ° C with a full spectrum of a 1PRK-2 lamp: For 10- 40 hours In this case, a polymer partially soluble in dimethylformamide falls out of solution. According to 20 IR spectroscopy and elemental analysis

You are fragile films of dark color. The yield of purified product is 78%. Example 4. Synthesized but the scheme

-C-OCH.

The obtained product can be prefilled with formula I. Subject of the invention 1. A process for the preparation of polymers by means of incorporation of bisazides and unsaturated compounds, characterized in that, to obtain polymers containing aziridine groups in the chain, monomers containing not less than two unsaturated bonds. 2. Method according to claim 1, characterized in that the reaction is carried out at a temperature of up to 100-160 ° C. 3. A method according to claim 1, characterized in that the reaction is carried out under the action of UV irradiation.