SU876663A1 - Method of producing polyarylates - Google Patents

Description

C54) - METHOD FOR OBTAINING POLYARRYLATES

one

The invention refers to the synthesis of high molecular weight polyarylates based on aliphatic dicarboxylic acids and bis-phenols, which can be used in various areas of the national economy, as film-forming and fiber-forming polymers.

Known is a method for preparing polyarylates based on the bis-phenols and di- | Q chlorides of aliphatic dicarboxylic acids in conditions interphase second polycondensation CllPoliarilaty obtained etim.sposobom have low viscosity characteristics of the high speed gydro- 15 Lisa acid chloride groups of aliphatic dicarboxylic acids water-alkaline solution, which leads to the cessation of chain growth of macromolecules.

The closest to the proposed technical essence and the achieved effect is a method for producing polyarylates by reacting derivatives of dicarboxylic acids. organic solvent in the presence of a tertiary amine 2.

In this way (solution polycondensation method) polyarylates based on di chlorine and aromatic acid and bisphenol hydrides have high concentrations of

Bone characteristics and have good film-and fiber-forming properties.

Polyarylates with low viscosity characteristics are obtained by dissolving polycondensation on the basis of aliphatic acid dichloroanhydrides, which is caused by the occurrence of side processes of ketene formation in the interaction of acids with tertiary amines, and having a heterogeneous, diversified polymer chain structure. .

The purpose of the invention is to simplify the process technology.

The goal is achieved by the fact that in the method of producing polyarylates by reacting dicarboxylic acid derivatives in an organic solvent medium in the presence of a tertiary amine, aliphatic dicarboxylic acid derivatives of general formula V are used as derivatives of dicarboxylic acids

X - CCA -R- CCA - X wheredec - (SCO) (p. 1-8),

X -

but

/ co-s Mr. (I

-CO-CHt

well a

and the process is carried out at 25-65 C.

The viscosity characteristics of the polyesters obtained are 0.22-0.94 dl / g, depending on the nature of the activating group and the conditions of polyester synthesis.

The polyethers obtained are soluble in 1,2-dichloroethane, NN-dimethylacetamide, hexamethylphosphoramide, M-methyl-2-pyrrolidone, dimethyl sulfoxide, forming highly concentrated solutions.

Their 10% solutions of polyesters in 1,2-dichloroethane by casting onto glass substrates are films with a tensile strength of 800–1200 kg / cm and an elongation of 5–10%.

Example 1. K 2.39 g (0.005 mol} bis-2,4-dinitrophenyl adipate) 1.59 g (0.005 mol) of phenolphthalein, 5.5 ml of 1,2-dIchloroethane and 2.8 ml of triethylamine (concentration 0.6 mol / l. The reaction mixture is stirred at 3 hours. The viscous reaction solution is poured into alcohol, the precipitated polymer is filtered off and extracted with ethyl acetate in Soxlet apparatus, then dried. Yield 97%, tnP 0.94 dl / g in 1,2-dichloroethane at 25 s, C 0.5 g / dl.

Example 2. Synthesis of the polymer was carried out in accordance with the procedure described in Example 1, but using bis-2, dinitrophenyl ester of succinic acid, as the diester. The reaction mixture is stirred at 1 h and then at 25 s for 2 h. The polymer yield is 97%, tnp / dl / g in 1,2-dichloroethane at 25 ° С 0.5 g / dl.

Example 3. Synthesis of the polymer is carried out in accordance with the procedure described in Example 1, but methyl ethyl ketone is used as the solvent. The reaction mixture was stirred at 50 ° C for 0.5 h, and then at for 2.5 h. The polymer yield 98%, tnp 0.82 DL / g in 1,2 dichloroethane at 25 ° C, C 0.5 g / dl

Example 4. Synthesis of the polymer was carried out in accordance with the procedure described in Example 1, but benzene was used as the solvent. The reaction mixture was stirred for 1 hour and then at 25 ° C for 2 hours. The polymer yield, d = 0.58 dl / g in 1.2 dichloroethane at 25 ° C, 0.5 g / dl. EXAMPLE 5 Polymer synthesis was carried out in accordance with the procedure described in Example 1, but b-c-p-nitrophenyl adipate was used as the diester. Reaction mixture

stirred at 65 ° C for 1 hour and then at 25 ° C for 2 hours. The polymer yield is 92%, p 0.38 dl / g. in 1,2-dichloroethane at 25 s, C 0.5 g / dl. ,

EXAMPLE 6 Polymer Synthesis Carried out in accordance with the procedure described in Example 1, but α-bis-pentachlorophenyl adipate is used as a diester. The reaction mixture was stirred at 65 ° C for 2 h, and then for 1.4. The polymer yield is 93%, tnp -0.29 dl / g in 1,2-dichloroethane at 25 s, С 0, .5 g / dl.

Example 7. Synthesis of the polymer was carried out in the same manner as in Example 1, but using bis-N-hydroxysuccinimidadipate as the diester. Polymer yield 94%, tnP 0.28 dl / g in 1,2-dichloroethane at 250 s, C 0.5 g / dl.

Example 8. Synthesis of a polymer was carried out in the same manner as in Example 1, but dimethyl sulfoxide was used as the solvent. The polymer yield 93%, LPR 0.26 DL / g in 1,2-dichloroethane at 25 ° C, 0.5 g / dL.

Example 9. Synthesis of the polymer was carried out in accordance with the procedure described in Example 1, but N, N-dimethylacetamide was used as the solvent. The polymer yield 91%, tnp 0,22 DL / g in 1,2-dichloroethane at 25 C, 5 g / dL.

Example 10. Synthesis of the polymer was carried out in accordance with the procedure described in Example 1, but using diane as the bis-phenol. The polymer yield is 96%, 1pr 0.82 DL / g in 1, 2-dichloroethane at 25 ° С, 5 g / d

EXAMPLE 11-16. The synthesis of polyesters is carried out in accordance with Example 1, but the bis-2,4-dinitrophenyl esters of malonic, glutaric, pimelic, pithic, azelaic, sebacic acids are used as the diester.

Example 17. Synthesis of polyester was carried out in the presence of an aliphatic 1,3-propanediOl. To a mixture of 2.39 g (0.005 mol) of bis-2,4-dini7 trofenyl adipate, 1.59 g (0.005 mol of phenolphthalein 2.8 ml: triethylamine in 5.5 ml of 1,2-dichloroethane was added 0.76 g ( 0.01 mol) 1,3-propanediol and the reaction mixture is stirred at 25 ° C for 3 hours. A polymer is obtained with a yield of 96%, 1% 0.88 dl / g in 1,2-dichloroethane at 25 ° C, 5 g / long

The formation of a high molecular weight polyester with a 3: 1 diol: activated ester ratio indicates the absence of interaction between the activated diester and aliphatic hydroxyl groups. Otherwise, as a result of a violation of equimolarity,

S876663

only poor molecular molecules of activated diesters are formed.

products. with dichlorohydrin.

This example demonstrates the opolyarylates obtained in examples

highly selective acyrued in Spo-1-17 are shown in the table.

 Synthesis conditions and characteristics

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Claims (2)

b) The proposed method allows to synthesize high molecular weight polyethers based on aliphatic dicarboxylic acids, the high selectivity of the method (aromatic hydroxyl groups are acylated and not aliphatic) allows you to synthesize regular Polyethers / film-like and fibrous groups, and their properties. no flow - side processes of interaction of diesters with tritic amines and hydrolysis reactions of functional groups). Thus, using as derivatives of dicarboxylic acids diesters of aliphatic dicarboxylic acids of general formula I in the method of producing polyarylates allows to simplify the process. Formula of the invention The method of obtaining polyarylates by reacting derivatives of di-carboxylic acids in organic solvent in the presence of a tertiary amine, differs from In order to simplify the process technology, aliphatic diarboxylic acid diesters are used as derivatives of dicarboxylic acids. X - OCO - R; - OCO - X, de R - (CH2) g, (p-1-8), X- - CO-SNg g, and the process is carried out at 25-65 C. Information sources, taken into account in the examination of 1. mrgan PU Polycondensation processes of polymer synthesis. M., Himi, 1970, p. 312. 2. Korshak V.V. et al. Non-equilibrium polycondensation, M., Nauka, 1972 p. 164 (prototype)