Aromatic polyester sulphone ketones

FIELD: chemistry.

SUBSTANCE: invention refers to high-molecular compounds, namely to aromatic polyester sulphone ketones of formula

(I),

;;;,

wherein n=1-20, z=2-50 for structural and film applications.

EFFECT: invention enables increasing fire, heat and thermal stability and mechanical characteristics of aromatic polyester sulphone ketones.

12 ex

 

The invention relates to macromolecular compounds, namely aromatic polyethersulphone structural and film destination.

Known aromatic polyethersulfone on the basis of various monomers and oligomers.

1. Sheng Shou-Ri, Luo Qiu-Yan, Yi-Huo, Luo Zhuo, Liu Xiao-Ling, Song Cai-Sheng. Synthesis and properties of soluble in organic solvents of aromatic polyetherketones containing a lateral methyl group and sulfonic connection. Synthesis and properties of novel organosoluble aromatic poly(ether ketone)s containing pendant methyl groups and sulfone linkages. J. Appl. Polym. Sci 2008... 107, No. 1, pp. 683-687.

2. Osano Keiichi, Sudipto Das, Turner Richard S. Synthesis and properties of polyetherketoneketone containing cyclohexyl. Synthesis and characterization of cyclohexyl-containing poly(ether ketone sulfone)s. Polymer. 2009. 50, No. 5, pp. 1144-1149.

3. Huang Zhen-Zhong, Yu La-Mei, Sheng Shou-Ri, Ge Wei-Wei, Liu Xiao-Ling, Song Cai-Sheng. Synthesis and properties of soluble polyetherketoneketone containing simple ether linkages and having a side group containing a few chlorine atoms. Synthesis and characterization of novel soluble poly(ether ketone sulfone)s with pendant polychloro groups. J. Appl. Polym. Sci 2008... 108, No. 2, pp. 1049-1054.

4. RF patent №2477292. Aromatic block-apoliticality. Publ. 10.03.2013. Bul. No. 7.

5. RF patent №2476453. Aromatic block-saponification. Publ. 27.02.2013. Bul. No. 6.

The main disadvantage of these polyesters is their low resistance.

The structure and properties closer to the proposed �Subramaniam, are polyesters based on a variety of bisphenol oligoethers and equimolar mixture of dichlorohydrin ISO - and terephthalic acids. [RF patent №2436762. Aromatic apoliticality and the method of their preparation. Publ. 20.12.2011]

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

The task of the invention is to provide polyesters with improved characteristics of heat, thermal, fire resistance, deformation-strength properties.

The problem is solved by obtaining aromatic polyethersulfones following formula

where n=1-20; z=2-50;

;;

;

the interaction of oligourethanes formula

with degrees of condensation n=1-20 with dichlorohydrin terephthalic acid, dichlorohydrin isophthalic acid, equimolar mixture of dichlorohydrin ISO - and terephthalic acids or dichlorohydrin 1,1-dichloro-2,2-di(n-carboxyphenyl)ethylene. The proposed polyesters are characterized by an increased rate of fire, heat, thermal stability and deformation-strength properties.

Synthesis of aromatic polyethersulfones following �the company.

Example 1. In a three-neck flask download 21,8261 g (0.01 mol) of oligourethane with n=1, 100 ml of dichloroethane, and 2.8 ml (0.02 mol) of triethylamine and while stirring add 3,7406 g (0.01 mol) of dichlorohydrin 1,1-dichloro-2,2-(n-carboxyphenyl)ethylene. The reaction is conducted at room conditions for 1 h. the Obtained polymer solution is diluted with 100 ml. of ethylene dichloride and visidot in isopropyl alcohol. Polyester is filtered off, washed with water from traces of hydrochloric acid of triethylamine, and dried in vacuo at 100°C for 48 h. the Yield is 95-98%, the viscosity of 0.7-0.8 DL/g (z=20-30, n=1).

Example 2. In a three-neck flask download 16,4555 g (0.001 mole) of oligourethane with n=10, 100 ml of dichloroethane, of 0.28 ml (0,002 mol) of triethylamine and while stirring add 0,3741 g (0.001 mole) of dichlorohydrin 1,1-dichloro-2,2-(n-carboxyphenyl)ethylene. The reaction is conducted at room conditions for 1 h. the Obtained polymer solution is diluted with 100 ml of dichloroethane and visidot in isopropyl alcohol. Polyester is filtered off, washed with water from traces of hydrochloric acid of triethylamine, and dried in vacuo at 100°C for 48 h. the Yield is 95-98%, the viscosity of 0.7-0.8 DL/g (z=3-4, n=10).

Example 3. In a three-neck flask download 31,7051 g (0.001 mole) of oligourethane with n=20, 100 ml of dichloroethane, of 0.28 ml (0,002 mol) of triethylamine and while stirring add 0,3741 g (0.001 mole) of dichlorohydrin 1,1-dichloro-2,2-(n-carboxyphenyl�)ethylene. The reaction is conducted at room conditions for 1 h. the Obtained polymer solution is diluted with 100 ml of dichloroethane and visidot in isopropyl alcohol. Block-copolyester was filtered, washed with water from traces of hydrochloric acid of triethylamine, and dried in vacuo at 100°C for 48 h. the Yield is 95-98%, the viscosity of 0.7-0.8 DL/g (z=2-3, n=20).

Example 4. In a three-neck flask download 21,8261 g (0.01 mol) of oligourethane with n=1, 100 ml of dichloroethane, and 2.8 ml (0.02 mol) of triethylamine and while stirring add 2,0303 g (0.01 mol) equimolar mixture of dichlorohydrin ISO - and terephthalic acids. The reaction is conducted at room conditions for 1 h. the Obtained dense polymer solution is diluted with 100 ml of dichloroethane and visidot in isopropyl alcohol. Polyester is filtered off, washed with water from traces of hydrochloric acid of triethylamine, and dried in vacuo at 100°C for 48 h. the Yield is 95-98%, the viscosity of 0.7-0.8 DL/g (z=20-30, n=1).

Example 5. In a three-neck flask download 16,4555 g (0.001 mole) of oligourethane with n=10, 100 ml of dichloroethane, of 0.28 ml (0,002 mol) of triethylamine and while stirring add 0,2030 g (0.001 mole) equimolar mixture of dichlorohydrin ISO - and terephthalic acids. The reaction is conducted at room conditions for 1 h. the Obtained polymer solution is diluted with 100 ml of dichloroethane and visidot in isopropyl alcohol. Polyester is filtered off, washed�t water from traces of hydrochloric acid of triethylamine, and dried in vacuo at 100°C for 48 h. The output is 94-98%, the viscosity of 0.7-0.8 DL/g (z=3-4, n=10).

Example 6. In a three-neck flask download 31,7051 g (0.001 mole) of oligourethane with n=20, 100 ml of dichloroethane, of 0.28 ml (0,002 mol) of triethylamine and while stirring add 0,2030 g (0.001 mole) equimolar mixture of dichlorohydrin ISO - and terephthalic acids. The reaction is conducted at room conditions for 1 h. the Obtained polymer solution is diluted with 100 ml of dichloroethane and visidot in isopropyl alcohol. Polyester is filtered off, washed with water from traces of hydrochloric acid of triethylamine, and dried in vacuo at 100°C for 48 h. the Yield is 95-98%, the viscosity of 0.6-0.7 DL/g (z=2-3, n=20).

Example 7. In a three-neck flask download 21,8261 g (0.01 mol) of oligourethane with n=1, 100 ml of dichloroethane, and 2.8 ml (0.02 mol) of triethylamine and while stirring add 2,0303 g (0.01 mol) of dichlorohydrin terephthalic acid. The reaction is conducted at room conditions for 1 h. the Obtained polymer solution is diluted with 100 ml of dichloroethane and visidot in isopropyl alcohol. Polyester is filtered off, washed with water from traces of hydrochloric acid of triethylamine, and dried in vacuo at 100°C for 48 h. the Output is 97-98%, the viscosity of 0.8 to 0.9 DL/g (z=20-30, n=1).

Example 8. In a three-neck flask download 16,4555 g (0.001 mole) of oligourethane with n=10, 100 ml of dichloroethane, of 0.28 ml (0,002 mol) of triethylamine and while stirring add 0,2030 g (0,001 �ol) dichlorohydrin terephthalic acid. The reaction is conducted at room conditions for 1 h. the Obtained polymer solution is diluted with 100 ml of dichloroethane and visidot in isopropyl alcohol. Polyester is filtered off, washed with water from traces of hydrochloric acid of triethylamine, and dried in vacuo at 100°C for 48 h. the Output is 97-98%, the viscosity of 0.8 to 0.9 DL/g (z=3-4, n=10).

Example 9. In a three-neck flask download 31,7051 g (0.001 mole) of oligourethane with n=20, 100 ml of dichloroethane, of 0.28 ml (0,002 mol) of triethylamine and while stirring add 0,2030 g (0.001 mole) of dichlorohydrin terephthalic acid. The reaction is conducted at room conditions for 1 h. the Solution was diluted with 100 ml of dichloroethane and visidot in isopropyl alcohol. Polyester is filtered off, washed with water from traces of hydrochloric acid of triethylamine, and dried in vacuo at 100°C for 48 h. the Output is 96-97%, the viscosity of 0.7-0.8 DL/g (z=2-3, n=20).

Example 10. In a three-neck flask download 21,8261 g (0.01 mol) of oligourethane with n=1, 100 ml of dichloroethane, 2.8 ml (0.04 mole) of triethylamine and while stirring add 2,0303 g (0.01 mol) of dichlorohydrin isophthalic acid. The reaction is conducted at room conditions for 1 h. a Solution of polymer was diluted with 100 ml of dichloroethane and visidot in isopropyl alcohol. Polyester is filtered off, washed with water from traces of hydrochloric acid of triethylamine, and dried in vacuo at 100°C for 48 h. the Yield is 95 to 97%,the viscosity - 0.6 to 0.8 DL/g (z=20-25, n=1).

In a three-neck flask download 16,4555 g (0.001 mole) of oligourethane with n=10, 100 ml of dichloroethane, of 0.28 ml (0,002 mol) of triethylamine and while stirring add 0,2030 g (0.001 mole) of dichlorohydrin isophthalic acid. The reaction is conducted at room conditions for 1 h. a Solution of polymer was diluted with 100 ml of dichloroethane and visidot in isopropyl alcohol. Polyester is filtered off, washed with water from traces of hydrochloric acid of triethylamine, and dried in vacuo at 100°C for 48 h. the Yield is 95 to 97%, the viscosity of 0.6-0.7 DL/g (z=3-4, n=10).

Example 12. In a three-neck flask download 31,7051 g (0.001 mole) of oligourethane with n=20, 100 ml of dichloroethane, of 0.28 ml (0,002 mol) of triethylamine and while stirring add 0,2030 g (0.001 mole) of dichlorohydrin isophthalic acid. The reaction is conducted at room conditions for 1 h. the Obtained polymer solution is diluted with 100 ml. of ethylene dichloride and visidot in isopropyl alcohol. Polyester is filtered off, washed with water from traces of hydrochloric acid of triethylamine, and dried in vacuo at 100°C for 48 h. the Yield is 95 to 97%, given the viscosity of 0.5-0.6 DL/g (z=2-3, n=20).

Below are given some properties of aromatic polyethersulfones obtained in examples 1-12.

PolymersTwith, °CKI %σp, MPAε, %
Example 127138655,0103,211,3
Example 226641956,0109,69,6
Example 326044157,5119,09,0
Example 424337550,099,415,0
Example 524440653,5104,014,7
Example 624041653,0106,914,1
Example 7 25639054,0106,012,2
Example 825041554,5110,511,0
Example 925242154,5116,611,4
Example 1022338753,586,116,8
Example 1121539853,087,614,4
Example 1221740354,093,313,9

The structure of aromatic polyethersulfones confirmed by IR spectroscopy. In the IR spectra are absorption bands corresponding to simple and complex terrestrial relations, dichlorethylene group, Ar-Br links, and sulfo and ketogroup�am and there are no bands for hydroxyl groups, which confirms the absence of traces of oligoethers in polymer sample and the formation of polymers expected structure. The results of turbidimetric titration also confirm the proposed structure. The curves turbidimetric titration has only one maximum, which confirms the absence of a mixture of polymers.

The technical result of the invention consists in the production of aromatic polyesters with high heat, heat, heat resistance and mechanical characteristics.

Aromatic polyethersulfones formula

where n=1-20; z=2-50;
;;
;



 

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