RU2201942C2 - Method for production of unsaturated oligoarylether ketones - Google Patents

Abstract

FIELD: industrial organic synthesis. SUBSTANCE: oligoarylether ketones that can be used for production of various-destination heat-resistant polymers ate prepared from aromatic ethers by condensing them directly with maleic anhydride in presence of AlCl₃ catalyst. EFFECT: simplified production of unsaturated aromatic oligomers. 7 ex

Description

 The invention relates to the field of production of unsaturated oligoaryl ether ketones, which can be used to produce heat-resistant polymers in mechanical engineering, aviation, electronics and other technical fields.

The synthesis of unsaturated oligoaryl ether sulfones by the method of high-temperature polycondensation of the disodium salt of an allyl-containing monomer and 4,4'-dichlorodiphenyl sulfone is known. Unsaturated maleimide-terminated oligoaryl ether sulfones were obtained by reacting 4,4'-dichlorodiphenyl sulfone with N- (4-hydroxyphenyl) maleimide in the presence of K ₂ CO ₃ .

 Unsaturated oligoaryl ether maleimides are synthesized by the reaction of tetracarboxylic acid dianhydrides with aromatic diamines and maleic anhydride. Similar unsaturated oligomers are also obtained by the reaction of n-phenylenediamine, dicarboxylic acid dianhydrides and unsaturated dicarboxylic acids (Shustov GB, Vologirov AK, Melnikov Yu.V. Unsaturated oligoestersulfones. // 5th All-Union Conference on Chemistry and Physicist Chernogolovka. - 1994. - 142 p .; Zhang Liantai, Gu Yi Jian Luxia Preparation characterization on reaction of poly (arylene ether sulphone) oligomers terminated active functional groups. // MACROAKRON'94. 35 IUPAC Int. Union Pure and Appl. Chem. Int. Symp. Macromol. - Acron, Ohio, 1994. P.561; Lyubchenko N.P., Arkhipova I.A., Dzhiksieva T.G. et al. Oligomaleiimides of aromatic tetracarbo acids with ether groups. // 4 All-Union Conference on the Chemistry and Physicochemistry of Oligomers. Nalchik. - 1990. - 198 p .; Patent 4684714, MKI C 08 G 69/26, NCI 528/353. Method for making polyimide oligomers. Lubowitz Human R., Sheppard Clude H .; The Boeing Co. Publ. 08/08/87).

Closest to the proposed is a method for producing oligoaryl ether ketones with terminal maleimide groups by reacting aromatic esters with dicarboxylic acid dichlorides and a telogen in the presence of an AlCl ₃ catalyst (Patent of Ukraine 28051, MKI 6 C 08 G 8/02. Method for producing oligo aryl ether ketones with terminal maleim groups. .F., Golovan S.V., Malysheva T.L. Publ. 16.10.2000).

 Derivatives of maleic anhydride (N-phenylmaleimide) are used as telogen.

 However, the above method suggests the use of the starting components, the synthesis of which is rather complicated (N-phenylmaleimide, dicarboxylic acid dichlorides).

 The objective of the invention is to simplify the method of obtaining unsaturated aromatic oligomers.

The objective is achieved in that in the method for producing unsaturated oligo aryl ether ketones based on the AlCl ₃ catalyst according to the invention, the synthesis of unsaturated oligo aryl ether ketones is carried out by reacting aromatic esters directly with maleic anhydride.

где Х - О, О-Ar-O, O-Ar-Y-Ar-O;
Y - O, SO, SO₂, CO-Ar-CO и другие подобные радикалы.The reaction is carried out according to the scheme.

where X is O, O-Ar-O, O-Ar-Y-Ar-O;
Y is O, SO, SO ₂ , CO-Ar-CO and other similar radicals.

 Diphenyl ether, 1,4-diphenoxybenzene, 1,3-diphenoxybenzene, 4,4-diphenoxydiphenyl ether, 4,4-bis (phenoxy) diphenylsulfone, 4,4-bis (phenoxy) diphenylsulfoxide, 4,4 are used as aromatic esters. bis (phenoxy) benzophenone, 1,4-bis (4-phenoxybenzoyl) benzene, 2,2-bis (4-phenoxyphenyl) propane, as well as compounds with terminal phenoxy groups obtained by the Friedel-Crafts reaction by the interaction of an excess of diphenyl ether with compounds containing active halides such as thionyl chloride, dicarboxylic acid chlorides (isophthalic, tereft Eva et al.).

 With an excess of one of the components, end groups are determined by this component.

 The proposed method for producing unsaturated oligomers is characterized in that aromatic esters interact directly with maleic anhydride, but not with its derivatives and dicarboxylic acid dichlorides, as in the prototype.

 Example 1

19.6 g (0.2 mol) of maleic anhydride and 17 g (0.1 mol) of diphenyl ether in 200 ml of chloroform are charged into a reactor equipped with a stirrer and reflux condenser. The reaction mixture is stirred until the reagents are completely dissolved and 69.4 g (0.52 mol) of AlCl ₃ are added. The reaction is carried out for 5-6 hours at a temperature of 20 ^o C and 5-6 hours at a temperature of 40-60 ^o C. Then chloroform is distilled off and 300 ml of a 3.5% solution of Hcl are added. Maintain the mixture at a temperature of 80-90 ^o C for 2-3 hours. The precipitate is filtered off, washed and dried to constant weight. A product is obtained with a yield of 78% in the form of a powder with a melting point of 104 ^° C. The structure of the obtained oligomer is confirmed by infrared spectroscopy. The characteristic band γ = 3100 cm ^-1 corresponds to stretching vibrations of the = CH group, γ = 1680 cm ^-1 corresponds to vibrations of -C = O ketone group, γ = 1760 cm ^-1 to vibrations of -C = O of the carboxyl group. The content of terminal carboxyl groups, determined by chemical analysis, is 19.9% (calculated value based on the ratio of components is 23.3%). The resulting substance is soluble in organic solvents of medium polarity, in an aqueous solution of soda.

 Example 2

In a reactor equipped with a stirrer and reflux condenser, 9.8 g (0.1 mol) of maleic anhydride and 17 g (0.1 mol) of diphenyl ether in 150 ml of 1,2-dichloroethane are charged. The reaction mixture is stirred until the reagents are completely dissolved and 34.7 g (0.26 mol) of AlCl ₃ are added. The synthesis was carried out analogously to example 1. The obtained oligomer is a powdery substance with a yield by mass of 70%, characteristic viscosity in DMF η = 0.024 m ³ / kg Softening point 185 ^o C. The product is soluble in DMF and in mineral acids (H ₂ SO _{4 end} ).

The structure of the obtained oligomer is confirmed by IR spectroscopy data on the presence of characteristic bands γ = 3100 cm ^-1 (-CH =) and γ = 1680 cm ^-1 (C = O ketone group) and a weak band γ = 1760 cm ^-1 , corresponding to the carboxyl group . The concentration of terminal carboxyl groups determined by chemical analysis is 3.5%.

The unsaturated oligoaryletherketone obtained in this example is capable of being converted into a crosslinked polymer upon heating. So, when it is heated for 6-7 hours in the temperature range from 150 ^o C to 200 ^o C, a polymer is formed, insoluble in H ₂ SO _{4 end} . The almost complete polymerization of double bonds is confirmed by IR spectroscopy. In the obtained cross-linked polymer there is no band of 3100 cm ^-1 (-CH =). The oligomer is also able to cure by the reaction of double bonds with amines. For example: 12 g of oligomer and 5 g of diaminodiphenyl oxide are dissolved in DMF and a uniform transparent film is obtained from a 50% solution. When it is heated with a constant increase in temperature from 150 ^o C to 250 ^o C for 8-9 hours, a polymer is obtained, on the IR spectrum of which there are no bands of 3100 cm ^-1 (-CH =) and 3400 cm ^-1 (stretching vibrations of NH ₂ groups). The resulting crosslinked polymer is insoluble in H ₂ SO _{4 conc} . According to TGA at a temperature of 400 ^o With the polymer loses 5% in weight.

 Example 3

9.8 g (0.1 mol) of maleic anhydride and 20.4 g (0.12 mol) of diphenyl ether in 170 ml of methylene chloride are charged to a reactor equipped with a stirrer and reflux condenser. The reaction mixture is stirred until the reagents are completely dissolved and 34.7 g (0.26 mol) of AlCl ₃ are added. The synthesis was carried out analogously to example 1. An oligomer was obtained with a yield by weight of 75%, which is a powdery substance with a softening temperature of 170 ^{° C.} and a characteristic viscosity η = 0.021 m ³ / kg. In the IR spectrum of the obtained sample there is practically no band at 1760 cm ^-1 corresponding to the carboxyl group. Thus, with an excess of diphenyl ether, an oligomer is obtained in which carboxyl groups are almost completely absent.

 Example 4

14.7 g (0.15 mol) of maleic anhydride and 26.2 g (0.1 mol) of 1,4-diphenoxybenzene in 170 ml of methylene chloride are charged to a reactor equipped with a stirrer and reflux condenser. The reaction mixture is stirred until the reagents are completely dissolved and 52 g (0.39 mol) of AlCl ₃ are added. The synthesis was carried out analogously to example 1. An oligomer was obtained with a yield by mass of 81%, which is a powdery substance with a softening temperature of 215 ^o C. The content of terminal carboxyl groups determined by chemical analysis is 9.8% (calculated value based on the ratio of components is 11, 2%). The resulting substance is soluble in DMF and mineral acids.

 Example 5

Aromatic ether is synthesized by the Friedel-Crafts reaction from diphenyl ether and thionyl chloride as follows. 11.9 g (0.1 mol) of thionyl chloride and 34 g (0.2 mol) of diphenyl ether in 200 ml of chloroform are charged into a reactor equipped with a stirrer and reflux condenser. After the reagents were dissolved, 34.7 g (0.26 mol) of AlCl _{3 were} added. The reaction is carried out for 5-6 hours at 20 ^o C. Then the solvent is removed and 250 ml of 3.5% Hcl are added. The mixture is kept until complete destruction of the complex with AlCl ₃ when the mixture is cooled to a temperature of 10-15 ^o C. Then the precipitate is filtered off and dried to constant weight. The product is obtained in practically quantitative yield, containing according to the IR spectra of the group S = O. The absence of SOCl and SOOH groups was confirmed by chemical analysis and IR spectroscopy.

The resulting aromatic ether in an amount of 36.5 g (0.095 mol) is loaded into a reactor equipped with a stirrer and reflux condenser, and 9.3 g (0.095 mol) of maleic anhydride in 250 ml of chloroform are added. The reaction mixture is stirred until the reagents are completely dissolved and 33.0 g (0.247 mol) of AlCl ₃ are added. Further, the reaction is carried out analogously to example 1. The reaction product (yield 84%) is a powdery substance with a softening temperature of 240 ^o C. Unsaturated oligoaryl ether ketone is soluble in hot DMF. The structure is confirmed by IR spectroscopy.

 Example 6

Aromatic ether is synthesized by the Friedel-Crafts reaction from diphenyl ether and isophthalic acid chloride as follows. In a reactor equipped with a stirrer and reflux condenser, 20.3 g (0.1 mol) of isophthalic acid chloride and 34 g (0.2 mol) of diphenyl ether in 250 ml of chloroform are charged. After the reagents were dissolved, 34.7 g (0.26 mol) of AlCl _{3 were} added. The reaction is carried out for 5-6 hours at 20 ^o C. Then the solvent is removed and 250 ml of 3.5% Hcl are added. The mixture is kept until complete destruction of the complex with AlCl ₃ with cooling to a temperature of 10-15 ^o C. The precipitate is filtered off and dried to constant weight. Get the product in almost quantitative yield. According to IR spectra, the product contains keto groups. The absence of acid chloride and carboxyl groups was confirmed by chemical analysis and IR spectroscopy.

The resulting aromatic ether in an amount of 43.7 g (0.092 mol) is loaded into a reactor equipped with a stirrer and reflux condenser, and 9.0 g (0.092 mol) of maleic anhydride in 300 ml of chloroform are added. The reaction mixture is stirred until the reagents are completely dissolved and 31.9 g (0.247 mol) of AlCl ₃ are added. Further, the reaction is carried out analogously to example 1. The reaction product (80% yield) is a powdery substance with a softening temperature of 240 ^o C. Unsaturated oligoaryl ether ketone is soluble in H ₂ SO _{4 end} . The structure is confirmed by IR spectroscopy.

 Example 7

38 g (0.1 mol) of 2,2-bis (4-phenoxyphenyl) propane and 9.8 g (0.1 mol) of maleic anhydride in 250 ml of chloroform are charged into a reactor equipped with a stirrer and reflux condenser. After the reagents were dissolved, 34.7 g (0.26 mol) of AlCl _{3 were} added. Further, the reaction is carried out analogously to example 1. The reaction product is a powdery substance with a mass yield of 77% and a softening temperature of 212 ^° C. The unsaturated oligoaryl ether ketone is soluble in H ₂ SO _{4 term} . The structure is confirmed by IR spectroscopy (γ = 3100 cm ^-1 for = CH-groups, γ = 1680 cm ^-1 for -C = O-groups).

 The resulting unsaturated oligoaryl ether ketones can be used as binders to obtain heat-resistant coatings and adhesives.

 Oligomers are capable of being converted into polymers by polymerization via unsaturated double bonds, both directly by thermopolymerization and in the presence of radical polymerization initiators. They turn into crosslinked polymers in the presence of hardeners with mobile hydrogen atoms (amines, polyols).

 The synthesized unsaturated oligoaryl ether ketones in their properties (solubility, heat resistance, softening temperature) are not inferior to the oligomers obtained by the prototype.

Claims (1)

A method for producing unsaturated aromatic ether oligo aryl ether ketones in the presence of an AlCl ₃ catalyst, characterized in that the synthesis of unsaturated oligo aryl ether ketones is carried out by condensing the aromatic esters directly with maleic anhydride.