SU398580A1 - METHOD OF OBTAINING PO.11IBG; FROM () KSL: Y.POV - Google Patents

Description

one

This invention relates to the manufacture of highly heat-resistant polymers.

A known method for the preparation of polybondyl oxazoles by the complete condensation of bis-o-aminophenols and 4,4-dipheiylphthalide dica, pboxylic acids in a polyphosphoric acid medium.

The polymers obtained are high molecular weight products that are soluble in a number of organic solvents, but due to the relative instability of lactone nickel, they are low heat resistant.

With the aim of obtaining more thermostable and soluble in organic solvents polymers, a method for the preparation of polybenzoxazoles by polycondensation of bis-aminophenols of the formula

/ G ™

Hnn

R- +

R

where RO-, -СЫ2-; RH-, CH3 2phenyl-3, 3-bis - (4-carboxyphenyl) -phthalimidium in the medium of nolyphosphoric acid (n о - 1,472-1,474).

Example 1. In a four-necked flask equipped with a mechanical bag with a 1 × 1L, equal to. A valve, barbatsr for argon supply, a thermometer, and a carbon chloride tube, were placed 2.3222 g (0.01 mol) of 3,3-diamino-4, 4 -duxyxnidenephenoxide, 4.4947 g (0.01 mol) of 2-phenyl-3,3-bis- (4-carboxyphenyl) -phthalyl 1idine and 57 g of full phosphoric acid.

The mass is stirred in a continuous stream of argon, the temperature is raised to 1bO ° C and carried on at this temperature for 5 hours. The reaction mass is discharged into ice water, the precipitated polymer is washed from polyphosphoric acid with water. After sunflower under vacuum at a temperature of 100-i05 ° C, the polymer yield is 6.06 (99.5% of the theoretical). The polymer is dissolved in N-methylpyrrolidone, tetrachloroethane, a mixture of tetrachloroethane with phenol, trncresol, hexamethylphosphoric triamide. The reduced viscosity of a 0.5% solution in N-methylpyrrolidone at 25 ° C is 1.8 dl / g. When heated in air, the polymer loses its weight at a temperature of 500 ° C and a heating rate of 4.5 deg / min 6%,

Paydeno,%: C 78.30: P 4.01: N 6.76.

(Cion.sNaOi).

Calculated,%: C 78.80: H 3.80; N 6.89.

4,4-diphephenylphthaliddiklrboxylic acids 1 1 and 3,3-dN4a-1, l-M, polymer, n-1, 3-mi, iiiii rii, chifaiyloxidl, is lost in

All at 470 ° C (atmosphere - nitrogen, heating rate 6 degrees Celsius) 7%.

Example 2. The reaction is carried out as described in Example 1. Source components: 3,3-diamino-4,4-dioxydiphenylmethane 2.3025 g (0.01 mol), 2-phenyl-3,3-bis- (4- carboxyphenyl) -phthalimidine 4.4947 g (0.01 mol), polyphosphoric acid 57 g

The polymer yield 6.03 g (99.2% of theoretical). The polymer is dissolved in N-methylpyrrolidone, tetrachloroethane, a mixture of tetrachloroethane and phenol, tricresol, hexamethylphosphoric triamide.

The reduced viscosity of a 0.5% polymer solution in -M-methylpyrrolidone at 25 ° C is 1.1 dl / g.

POLYMER loses 8% of its original weight in air at 500 ° C (heating rate 4.5 K / min).

Found,%: C 80.63; H 4.36; N 6.66.

(С41Н25№Оз) p.

Calculated,%: C 81.03; H 4.14; N 6.91.

Polybenzoxazole, obtained on the basis of 3,3 - diamine-4,4 - dioxydiphenylmethane and 4,4 - diphenylylphthalidicarboxylic acid, loses 12% of its original weight at 500 ° C and inert atmosphere (heating rate 6 ° / min).

Example 3. The reaction is carried out as described in Example 1. Starting components: 4,4-damino-3,3-dioxydiphenepne 2.1624 g (0.01 mol), 2-phenyl-3,3-bis- (4- carboxyphenyl) -falimidine 4.4J47 i (0.01. mol), polyphosphoric acid 57 g.

The polymer yield 5.87 g (99% of theoretical).

Polymer is dissolved in S-methylpyrrolidium, tetrachloroethane, tricresol, a mixture of tetrachloroethane and phenol.

The reduced viscosity of a 0.5% polymer solution in N-methylpyrrolidone at 25 ° C is 1.65 dl / g. The polymer loses 4% of its initial weight at 500 ° C in air (heating rate 4.5 K / min).

Paydeno,%: C, 80.28; P 3.99; N 6.86.

(G.oH23N ,, 03) “. Calcined,%: C, 80.93; P 3.90; N 7.07.

The polymer obtained on the basis of 4,4-diamine-3, 3-dioxydiphenyl and 4,4-dicarboxydiphenylphthalide loses 6% of the initial

polymer weight in an inert atmosphere with

480 ° C.

Subject invention

The method of producing polybenzoxazoles by

polycondensation of bis-o-aminophenols and dicarboxylic acids in polyphosphoric

acid when heated, characterized in

that in order to increase heat resistance and

solubility in organic solvents,

as dicarboxylic | 1 acid is used

2-feiyl - 3,3 - bis- (4-carboxyfeiyl) -phthalate-.

and mi din.