RU2466151C1 - Aromatic polyesters - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to aromatic polyesters used as structural and film materials. An aromatic polyester is a compound of formula:

in which

and n= 1-20, z=5-100.

EFFECT: said aromatic polyesters have high fire- and heat-resistance, as well as improved mechanical properties.

1 tbl, 12 ex

Description

The invention relates to macromolecular compounds, in particular to aromatic polyesters, which can be used as structural and film materials.

Aromatic polyesters based on various oligomers are known.

1. Kharaev A.M., Mikitaev AK, Kunizhev BI, et al. Synthesis and some properties of block copolyisulfanarylates based on oligosulfonophenolphthaleins. Navy, 1984, B14, p. 271-274.

2. Mikitaev A.K., Shustov GB, Kharaev A.M. et al. Synthesis and some properties of block copolyisulfonarylates. Navy, 1984, A1, pp. 75-78.

3. Shirokova LB, Storozhuk IP, Voishchev B.C. et al. Properties of irregular poly (arylate-arylene sulfonoxides) based on oligoarylene sulfonoxides with different degrees of polymerization. Navy, 1982, T24A, No. 9, pp. 1974-1980.

The main disadvantage of these polymers is their low fire resistance. Closer to the proposed inventions in structure and properties are polyesters based on diane oligoketones and phthalic acid dichloroanhydrides. S Ozden, A. M. Charaev, A. Shaov, The synthesis of polyetherketones and investigation of their properties. J. Mater. Sci, 1999, R 2741-2744.

However, these polymers have low physicochemical properties and low oxygen index values.

The objective of the invention is the creation of polyesters with increased values of fire, heat, heat resistance, as well as mechanical characteristics.

The problem is solved by obtaining aromatic polyesters of the following structure

Where

n is 1-20; z = 5-100

the interaction of oligoester based on 4,4'-dioxo-2,2-diphenylpropane and 1,1-dichloro-2,2-di (4-chlorophenyl) ethylene with different degrees of condensation n = 1-20 with an equimolar mixture of iso- and dichlorohydrides terephthalic acid, 1.1 dichloro-2,2-di (4-carboxyphenyl) ethylene chloride or 4,4'-difluorobenzophenone. The proposed polyesters are characterized by high rates of heat, thermal, fire resistance, as well as mechanical characteristics.

Synthesis of Aromatic Polyesters Based on Iso- and Terephthalic Acid Dichlorohydrides

EXAMPLE 1. In a two-necked conical flask with a capacity of 250 ml equipped with a mechanical stirrer, 7.0169 g (0.01 mol) of oligoester with n = 1 (molar mass = 701.6878) and 100 ml of dichloroethane are charged. 2.82 ml (0.02 mol) of triethylamine are poured with stirring. After complete dissolution of the oligomer, an equimolar mixture of iso- and terephthalic acid dichloransidrides in an amount of 2.0325 g (0.01 mol) is added to the reaction flask. The reaction is carried out at room temperature for 1 hour. The reaction mass is diluted with 100 ml of dichloroethane and the polymer is precipitated in isopropyl alcohol. The precipitate formed is filtered off and washed with distilled water until the chlorine ions are completely removed. The properties of the obtained polyester are given in the table.

Examples 2-4. The syntheses are carried out as in example 1, only oligomers with degrees of condensation n = 5 (molar mass = 2595.2782), n = 10 (molar mass = 4962.2662), n = 20 (molar mass) are taken as starting oligomers = 9696.2422). Synthesis of Aromatic Polyesters Based on 1,1-Dichloro-2,2-di (4-carboxyphenyl) Ethylene Dichlorohydride EXAMPLES 5-8. The synthesis is carried out according to examples 1-4, only instead of an equimolar mixture of iso- and terephthalic acid dichlorides, the corresponding amounts of 1,1-dichloro-2,2-di (4-carboxyphenyl) ethylene dichloride with a molecular weight of 374.05 are taken.

Synthesis of aromatic polyesters based on 4,4'-difluorobenzophenone

Example 9. In a 250 ml three-necked flask equipped with a mechanical stirrer, a Dean-Stark trap, reflux condenser, inert gas barter, 7.0169 g (0.01 mol) of oligoester with n = 1, 50 ml of dimethylacetamide, 50 ml are charged chlorobenzene 2.1820 g (0.01 mol) of 4,4'-difluorobenzophenone 1.79 g (0.013 mol) K ₂ CO ₃ The temperature of the reaction mixture was raised to 170 ° C and the synthesis was carried out under a stream of nitrogen for 6 hours. The reaction mass is diluted with 50 ml of dimethylacetamide and precipitated in distilled water. The polymer is washed with distilled water and dried to constant weight.

Examples 10-12. The syntheses are carried out according to example 9, only oligoesters with degrees of condensation n = 5 (example 10), n = 10 (example 11), n = 20 (example 12), in the same molar amounts as in example 9, are taken as dioxo compounds .

Table Some properties of aromatic polyesters Example No. η _ol , dl / g TST ° C TGA, ° C KI,% σ pit, MPa 2% fifty% one 1.4 197 397 550 38,0 73,4 2 1.3 205 390 550 38,0 73.9 3 1,0 210 403 570 39.0 75.1 four 1,1 213 410 595 39.5 75,5 5 1.3 200 410 570 42.0 90.2 6 1,0 204 413 597 42.5 90.9 7 1,0 213 417 610 42.5 92.2 8 1,2 215 422 624 43.0 93,4 9 1,1 189 410 584 38.5 87.7 10 1,2 196 410 592 39.5 89.4 eleven 1,2 201 421 598 39.5 90.3 12 0.9 208 408 610 40,0 87.8

Aromatic polyesters are stable in dilute solutions of mineral acids and alkalis. The structure of aromatic polyesters is confirmed by IR spectroscopy and turbidimetric titration. The IR spectra have absorption bands for simple and ester bonds and no bands for OH groups.

On the curves of turbidimetric titration there are only one maximum.

The technical result of the invention is to expand the range of aromatic polyesters with high heat and heat resistance, increased values of the oxygen index, high mechanical properties.

Claims (1)

Where

n is 1-20; z = 5-100.