SU390107A1 - METHOD FOR OBTAINING FLUORINE CONTAINING POLYMERS - Google Patents

Description

one

This invention relates to the field of production and OLI-dimensional materials, namely, fluorine-containing polymers, characterized by high chemical and thermal stability, and the preparation of polymers of fluorine-containing a-fluoroacrylic and methacrylic acid esters.

There is a known method for the preparation of the fume containing;

vHi.;

As can be seen from the formula, the initial monomers for the preparation of fluorine-containing polymers according to the proposed method contain in the efp of the radicals fup.k.

The present invention aims to produce reactive fluorine-containing polymers.

This goal is achieved by the radical polymerization of the new and xycene-containing fluorine-containing esters of the formula:

..eleven; ..

G11; .. G11G- C- i, i-CH-j

I about SNP i lCl

groups), which creates potential opportunities for further chemical and chemical synthesis of the polymers obtained, for example, for cross-linking, and other reactions. Thus, the proposed method, with one CTOpOiHbi, expands the range of fluorine-containing polimers, the number of which is still relatively small and, on the other hand, makes it possible to obtain fluorine-containing submersions from the reaction; nose, common npyniMH, carrying in them potential possibilities for subsequent chemical modifications of the resulting polymers in order to impart them, but; The latter feature of the proposed method favorably distinguishes it from the known methods of icing of yielded ferric-containing polymers of the described class.

Fluorine containing fields: they offer the method, which is obtained by polymerization of the initial molders in a block or solution by heating in an inert gas atmosphere and in the presence of known initiators of radical polymerization, for example, diazgryl bisazoisobutyric acid. As a result of polymerization, transparent soft rubber-like or solid glassy polymer is formed depending on the nature of the initial monomers: solids with glass transition temperatures from -1: 0 ° to 95 ° C and decomposition temperatures from 230 ° to 400 ° C (iHo thermomechanical curves ).

Polymer solution does not dissolve in organic solutions, but to varying degrees swell in some of them, for example in dimethylformamide, dioxane, tetrahydrofuran, chlorobenzene.

The polymers obtained according to the proposed method are burned in a gas burner, and they have the properties of self-extinguishing when they are removed from the flame. The exception is nol.mer of glycidyl-c-fluoroacrylate, which does not have a characteristic of SA: mypp.

Example 1. Obtaining polymer glycidyl-c-fcdcrylate in block

7.11 g of glycidyl ether (l-fluoroacrylic acid, in which SM was preliminarily dissolved 0.014 g (0.2 wt.%) Of dinitrile of azobisisobutyric acid, is heated in a zinc aa miule, in an atmosphere of dry arg. thinness: at a temperature of 30 ° - for 7 hours, at 40 ° - 15 hours,: at 50 ° - 10 hours. This forms a solid transparent colorless polymer. It is crushed and freed from monomer residues and low molecular weight fractions by extraction acetyl at its boiling point for 20 hours.After drying in vacuum at 50 ° to constant weight, 6.0 g (85% of theoretical) of glididyl-a-fluoro1-acrylate polymer in the form of a white powder, insoluble in common organic solvents and water, but not swelling slightly in dimethylformamide, dioxe, e. - about 400 °. Pa of thermomechanical curves of the polymer in the temperature range from 50 to 250 ° is observed a nonstene reduction in the deformation of the image, which is aggravated, SEEARCH, by stitching during the reaction of the eioxy groups. Above 250 ° at the terra; 1mexe1: what is a gradual increase in the deformation of the specimen, and this increase is insignificant - iri 400 ° it exceeds 15%.

In a gas-burning fire, the polymer burns with a TbiiM flame, it does not self-extinguish upon removal

out of fire.

Example 2. Obtaining polymer a-fluoroacrylic acid 1,1-dichloroisopropyl ester by block polymerization

25 g of 1,1-di. Chloroisopropyl 1-ether of α-fluoroacrylic acid, in which 0.05 g (0.2% by weight) of dinitrile of azobisisobutyric acid dinitrile is pre-dissolved, is heated in a sealed amulla in a dry argon atmosphere at a temperature of 40 ° within 3 hours This produces a solid and transparent colorless polymer. According to the thermo fur of the first curve for zero, the glass temperature of the glass transition is 85 ° and the flow temperature (with decomposition) is about 250 °.

The block polymer is crushed and freed from the residues of the monomer 5Hstreggirov1, and ccio ether (in which MOiHOMep is well dissolved) for boiling at its boiling point for 25 hours. The polymer obtained in the form of a white powder is dried at 60 ° under vacuum until it is very light. The yield is 22 grams, which is 88% of the theoretical. The powdered polymer has a temperature of about 100 °. Cloves of 95 ° and flow (with decomposition) are about 275 °. The polymer does not dissolve in organic solvents, it swells to a limited extent in tetrahydrofuran and dnmethylsulfate.

In the flame of a gas torch, PolymeP burns, however, it does not light up immediately, but after 5–6 sec, and when self-ignition is removed from the fire, it is lost.

Example 3. Obtaining polymer 1-chloro-1ox 1113opropyl ester of a-fluoroacrylic acid by solution polymerization

PacTBOiD 2.12 g of 1-chloro-1-hydroxy-isoionyl ester a-fluoroacrylic acid and 0.021 g (about 1 wt.%) Of azobisiso-butyric acid dinitrile in 50 ml of dry benzene are heated with stirring (in a current of dry argon with at a temperature of 70 ° C. During the polymerization, a white polymeric powder drops out of the solution, polymerization and dissolve after 30 ln / n, the polymer is filtered off, and washed with petroleum ether and dried in vacuo at 80 ° to constant weight. % of theoretical polymer in the form of a light yellow powder, not soluble in organic tvaritel x and water but nabuhak) 1I, with its long-term (2-3 weeks) standing or heating in tetragidpofurane, di etilfopma MEMBER dioxane. The glass transition temperature of a polymep is about 55 °, the flow (with decomposition) is about 230 °. The polymer is combustible, but it has the property of self-extinguishing when removed from the silt.

PRI me R 4. Obtaining polymer 1-chloro-1fa-fluoro-p-chloro-n-spionoxy) - nzoyropylmethacrylate in a block of 10.2 g of l-chloropl-l - ((.. -fluorop-pJ-hl;) pyroiol oxi ) - zopropyl methacrylate, in which pre-dissolved 0.02 g (0.2 wt.%) Of dinitrile azobisisoic acid, is heated in a stock vial in a dry argon atmosphere at 40 ° C for 10 hours, and 50 ° - 2 hours at 60 ° - 4 hours and at 70 ° - 10 hours.

In the polymerization process, a colorless solid and transparent polymer is formed. It is cleaned from residues of moayumer and impurity molecular molecules, extracting with petroleum ether (fraction 70-100 °) at a temperature of about 30 hours per hour. After drying in a vacuum of 50 ° C to constant weight, 6.8 g (68% of theoretical) of a white powdered polymer with a glass transition temperature of about 35 ° and a pour point (with decomposition) of about 275 ° (according to a thermomechanical curve) are obtained. The polymer is resistant to water, ethanol, betaisol, acetone, and a variety of other solvents, but swells in dimethylformamnde, dioxash, tetrahydrofuran.

The polymer burns in a fire, but is self-extinguishing when taken out of the flame.

Example 5. Obtaining polymer Loksn, 1 - (a-fluoro-p-chloropropio1 oxn) -isopronylmethacrylate in block

6.25 g monoMER in which

i-. dissolved 0,0125 g (0.2 wt.%) diiitrile

- azobisisobutyric acid, heated in an amnule in another in an atmosphere of dry argon

 Prn temperatures of 40, 50., 60, and 70 ° for

10 hours at each of the listed temperatures.

A colorless and rubber-like polymer (transparent) is formed. It is crushed and treated with dimethylformamide, in which the polymer swells strongly. The gel formed for 5 days is treated with an excess of cepiHoro ether and a white rubber-rich mass is obtained, the yield of which after drying in a vacuum of 70 ° C is 3.5 g (66% of the theoretical). The glass transition temperature of the polymer is 11 °, the flow temperature is OKolo 285 ° (according to thermomechanical; nic curves).

Polymer 1 does not dissolve in organic solvents, "o" slightly swells into tetrahydrofuranium, significantly - in dimethylformamide. It burns in a flame of a 1-burn burner, while it burns itself when it is removed from the fire.

Subject and purpose of

The method for producing fluorine-containing polymers based on unsaturated fluorine-containing esters by radical polymerization may be used in block or solution, characterized in that, in order to obtain reactive fluorine-containing polymers, MOFiMepOiB use ftsr: satures as a starting material.

H - (- S - S GN. II I

Oh X,

idi K -; SMZ at X-- G R-CH.-CH-GN, -. Clch.j

/ IfJU X CH ;,

p-C1CH2-CHF-C-0 -Cllv

Clchv

 fflCHHOCH,

CHTi.i

SUNGONR-e-O-CH-g

I: H0 OHN; C1.CH2