RU2556230C2 - Aromatic polyethersulphone ketones - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: claimed invention relates to aromatic polyethersulphone ketones. Described are aromatic polyethersulphone ketones of gotmula:

, where n = 1-20; z = 2-100; R =

,

.

EFFECT: obtaining aromatic polyethersulphone ketones with high indices of fire-, heat-, and thermal resistance and mechanical characteristics.

1 tbl, 6 ex

Description

The invention relates to macromolecular compounds, namely to aromatic polyethersulfonketones of structural and film purpose.

Aromatic polyethersulfonketones based on various monomers and oligomers are known.

1. Osano Keiichi, Das Sudipto, Turner Richard S. Synthesis and properties of polyetherketonsulfones containing cyclohexyl. Synthesis and characterization of cyclohexyl-containing poly (ether ketone sulfone) s. Polymer 2009. 50, N5, c. 1144-1149.

2. Huang Zhen-Zhong, Yu La-Mei, Sheng Shou-Ri, Ge Wei-Wei, Liu Xiao-Ling, Song Cai-Sheng. Synthesis and properties of soluble polyetherketonsulfones containing ether bonds and having side groups containing several chlorine atoms. Synthesis and characterization of novel soluble poly (ether ketone sulfone) s with pendant polychloro groups. J. Appl. Polym. Sci .. 2008.108, N 2, p. 1049-1054.

3. Sheng Shou-Ri, Luo Qiu-Yan, Yi-Huo, Luo Zhuo, Liu Xiao-Ling, Song Cai-Sheng. Synthesis and properties of soluble in organic solvents aromatic polyetherketones containing methyl lateral groups and sulfonic bonds. Synthesis and properties of novel organosoluble aromatic poly (ether ketone) s containing pendant methyl groups and sulfone linkages. J. Appl. Polym. Sci .. 2008.107, N 1, p. 683-687.

4. RF patent No. 2476453. Aromatic block copolyester ethers. Publ. 02/27/2013.

5. RF patent No. 2477292. Aromatic block copolyethersulfones. Publ. 03/10/2013. Bull. Number 7.

6. Kharaev A.M., Bazheva R.Ch., Khasbulatova Z.S., Begieva MB, Istepanova O.L., Istepanov M.I. Synthesis and properties of heat-resistant aromatic block copolyesters. University News. North Caucasus region. Natural sciences, 2007. No. 3. S.50-53.

The main disadvantage of these polyesters is their low fire resistance.

The structure and properties closer to the present invention are polyesters based on various diane and phenolphthalein oligoesters, RF patent No. 2436762. Aromatic copolyethersulfonketones and method for their preparation.

However, the latter are characterized by low mechanical and thermal characteristics, as well as low oxygen index values.

The objective of the invention is the creation of polyesters with enhanced characteristics of heat, heat, fire, deformation and strength properties.

The problem is solved by obtaining aromatic polyethersulfonketones of the following formula:

where n = 1-20; z is 2-100;

R =

the interaction of oligosulfonketones of the formula:

with degrees of condensation n = 1-20 (RF Patent No. 2458917. Publ. 20.08.2012 Bull. No. 23) with 4,4′-difluorodiphenyl ketone or 4,4′-dichlorodiphenyl sulfone in dimethyl sulfoxide.

The proposed polyesters are characterized by high rates of fire, heat, heat resistance and strength properties.

Heat treatment can structure the proposed polyethersulfonetone, which makes it possible to significantly increase the thermal and mechanical properties of polyethersulfonetetons.

The synthesis of polyethersulfonketones is carried out according to the examples.

Example 1. In a three-necked conical flask equipped with a mechanical stirrer, a Dean-Stark trap, a reflux condenser, an inert gas feed barber, 12.3584 g (0.01 mol) of oligosulfonketone with n = 1 (molecular weight = 1235.8413) are charged , 50 ml of dimethyl sulfoxide, 50 ml of toluene and 2.04 ml of 9.8 N. NaOH solution. The temperature of the reaction mass is raised to 140 ° C and the synthesis is carried out under a stream of inert gas (nitrogen or argon) to completely remove traces of water. After distillation of the azeotropic toluene: water mixture, the reaction mass is cooled to 70-80 ° C, 2.18203 (0.01 mol) of 4,4′-difluorobenzophenone (molecular weight = 218,203) are added. The reaction is carried out at a temperature of 170-180 ° C for 6 hours. The reaction mass is diluted with 150 ml of dimethyl sulfoxide and precipitated in distilled water. The precipitate formed is filtered off and washed with distilled water until the chlorine ions are completely removed and dried to constant weight.

Yield 98%, reduced viscosity = 1.0-1.1 dl / g, z = 45-50.

Example 2. The synthesis is carried out as in example 1, and as the oligomer is taken oligosulfonketone with n = 10 with a molecular weight of 10228,257.

The yield is 97%, the reduced viscosity is 0.9-0.95 dl / g, z = 4-7.

Example 3. The synthesis is carried out as in example 1, and as an oligomer is taken oligosulfonketone with n = 20 with a molecular weight of 19094,258.

Yield 96%, pref. viscosity = 0.8-0.9 dl / g, z = 2-4.

Example 4-6. The syntheses are carried out according to examples 1-3, and the corresponding amounts of 4,4′-dichlorodiphenyl sulfone (molecular weight = 285.8636) are taken as the dihalide.

Yields - 96-97%; Viscosity (pref.) = 0.7-0.9 dl / g, z = 45-50, 4-7, 2-4, respectively.

Below are some properties of aromatic polyethersulfonketones.

Polyethersulfonketone Properties

Polymers for example T _c , ° C TGA, ° C (2% weight loss) KI,% σ _p , MPA ε,% one 181 405 44.5 74,2 27.3 2 186 406 45.0 76.0 28.0 3 187 400 45.0 77.4 28,2 four 180 389 44.0 72.8 27.0 5 191 401 45.0 75.6 26.8 6 190 404 45.5 76.0 27.5

The structure of aromatic polyethersulfonketones is confirmed by IR spectroscopy. The IR spectra contain absorption bands corresponding to ether bonds, dichloroethylene, sulfo and keto groups, and there are no bands for hydroxyl groups. Turbidimetric titration results also confirm the proposed structure.

The technical result of the invention is to obtain thermosetting aromatic polyesters with high rates of fire, heat, heat resistance and mechanical characteristics.

Claims (1)

Aromatic polyethersulfonketones of the formula

where n = 1-20; z is 2-100;