SU755809A1 - Nitrogen-containing polymers as glass plastic material binders and hteir preparing method - Google Patents

Description

The invention relates to the production of thermally and heat-resistant nitrogen-containing polymers based on tetranitriles, aromatic tetracarboxylic acids and aromatic di-o-cyanamines of the general formula

magical tetracarboxylic acids and aromatic diamines obtained from phenol at 170-180 ° С

^№ Х ^с \ ₂ н _г -К-н " ₂ · ms"

II and

'ί Ar < ^s '? ΝΝΗ ΗΝΝ < ⁰ '

WITH

II

\\ /

cm

15

where k = -; -CH ₂ -; -about-;

N - I - Ν Ί - in and out!

N and

Ν - I - Ν

Di

However, a disadvantage of polymers is the relatively low stability of acids and alkalis.

indicated their action on the action

with η = 10-30, 25

which can be used as binders for glass-reinforced plastics, coatings, etc.

Macroheterocyclic polymers based on tetranitriles are known. The purpose of the invention is to obtain thermally and heat-resistant macroheterodically durable polymers with high hydrolytic stability *

755809 4

The goal is achieved by yem that are nitrogen-containing polymers of the formula

Ν - ^> ~ '-ό ^- ''

CM

where K = - -CH ₂ - -O-;

^Ar *) us *) 3-o- "СХ '

η = 10-30,

as a binder for fiberglass. The polymers receive in accordance with the following scheme.

NA

‘Ag / V

CH

+ 2H ₂ 1M

„Lg ⁿⁿ *.

YAP

μ V \\

SM Lch

The initial mixture of tetranitrile tetracarbonate acid and aromatic di-o-cyanamine, taken in a 1: 2 ratio, is poured with phenol, lithium chloride is added as a catalyst and the reaction is carried out until ammonia is released at 170-180 ° C (~ 30 hours). The polymer solution is poured into acetone, the precipitated precipitate is filtered off and dried. The polymers are brown to black powders. The reduced viscosity of the polymers in N-methylpyrrolidone is 0.1-0.3 dl / g at 25 ° and a concentration of 0.5%.

The structure of the obtained polymers is confirmed by the data of elemental analysis and IR spectroscopy. The IR spectra of polymers contain absorption bands, 9, cm ~ ¹ : 3300, 3200 (ΝΗ),

1660 (θ = Ν macrocycle, 1630 C ~ M quinazoline cycle and there are no absorption bands C = M. The polymers obtained have high heat resistance. According to the dynamic TGA, the temperature of the onset of their mass reduction in air is 450480 ° С.

The polymers can be processed into products under a pressure of 15-25 kg / cm ² at 250-350 ° C. The products thus obtained do not soften to the temperature of the intensive decomposition of the polymer (60 (1) ° C.

All polymers after synthesis are soluble in amide solvents.

Example 1. Polycondensation of tetranitrile with pyromellitic acid with 3,3 ', 4,4 ⁴ -dicyanodiaminodiphenyl oxide.

0.1782 g is loaded into a two-neck flask equipped with a capillary to introduce argon and a reflux condenser.

from tetranitrile of pyromellitic acid 0.5006 g (0.002G1) 3,3 ', 4,4-dicyanodiaminodiphenyloxide, 0.02 g and 10 ml of phenol. The mixture is then heated at 170-180 ° C until the evolution of ammonia stops (30 hours), after which the polymer solution is poured into acetone and the precipitated precipitate is filtered and dried. The polymer is soluble in amide solvents. The temperature of the beginning of the decrease in the mass of the polymer when it is heated in air at a rate of 5 deg / min is 480 ° C. The polymer yield 94%. The reduced viscosity in N-methylpyrrolidone [) ¹ )} 0.3 DL / g

(0.5% polymer solution at 25 ° C).

20 The polymer is processed into monolithic products at a pressure of 20–25 kg / cm and a temperature of 300 ° C. When the polymer is boiled for 15 min in a 5% solution of hydrochloric acid, the polymer completely retains all the properties, including the reduced viscosity in-methylpyrrolidone.

Example 2. Polycondensation of tetranitrile diphenyloxytetracar, 0 bonoic acid with 3,3,4,4-dicyanodiaminodiphenylmethane.

Polycondensation 0,2703g tetranitro difeniloksidtetrakarbonovoy acid with 0.4966 g of 3,3 *, 4,4-phenylmethane ditsianodi__ in analogy with ^e polymer measure 1. Yield 95%. Polymer

soluble in amide solvents, Capri ⁱⁿ при-methylpyrrolidone at 25 ° C at 0.2 dl / g (0.65% polymer solution). The onset temperature decreases

40 mass of the polymer when heated in air at a rate of 5 ° C / min is 47O ° C. The polymer is processed into monolithic products at a pressure of 15–20 kg / cm ² and 2500 (3).

45 the stability of the polymer obtained is similar to polymer 1.

Example 3. Polycondensation. tetranitrile pyromellitic acid with 3,3 ', 4,4', -dicycodiaminodiphenyl.

50

Polycondensation of 0.1732 g (0.001 M) of pyremelic acid tetranitrile with 0.4 6 84 g (0.002 M) 3,3 ', 4,4'-dicyanodiaminodiphenyl is carried out analogously to example 1. The polymer yield 97%. The polymer is soluble in N- methylpyrrolidone, 0.2 dl / g at 25 ^P С and 0.5% polymer concentration. The temperature of the beginning of the decrease in the mass of the polymer when heated in air at a rate of

YO 5 deg / min is 4 80 C. The polymer is processed into monolithic products at a pressure of 25 kg / cm ² and 300350 ° С. The hydrolytic stability of the polymer obtained is similar to polymers 1 nd 2.

755809

‘6

P ~ p and mer 4. Polycondensation of tetranitrile diphenylene sulfonic acid with 3, C ¹ , 4, 4-dicyanodiphenyl oxide.

Polycondensation of 0.3184 g (, ΟΟΙΜ) of tetranitrile diphenylsulfone of tetracarboxylic acid is carried out with 0.5006 g (0.002 M) 3, 3 ', 4,4-dicyanodiaminodiphenyl oxide as in Example 1. You are a polymer 90%. The polymer is soluble at

tilpirrolidone 0.3 dl / g (0.5% solution at 2?). The temperature of the beginning of the decrease in the mass of the polymer when it is heated in air at a rate of 5 deg / min is 450 °. The polymer is processed into products at a pressure of KZ 15 kg / cm ² and 250 ^o C. The hydrolytic stability of the obtained polymer is similar to polymers 1-3.

To confirm the structure of the polymers obtained, the table shows the elemental analysis data and the IR spectra.

in amide solvents. And _instilled in N-me10

When- Gross Elemen ' burnt measures Formula analysis calculated % X data found ' WITH. H N one WITH" 1G, Ν, 0 70.80 2.50 21.73 3200 (ΝΗ), 1660,, 1630 Hey 1b 6 9.54 3.07 20.95 (c = k) , 1260 (-O-) 2 ^From 46 7 5.50 75.12 3.17 3.49 19.14 18.32 3300 (s = y (NN) ·, 1660,1630 3 WITH "And, Ν,„ 74, 50 2 ^ 63 22.86 3300 (ΝΗ) 1660.1620 Zy Ίί> ίο 73.22 3.17 22.05 (s = n) four with Η Ν 0., 5 70.30 2.55 18.63 3200 (NN) ·, 1660,1630 44 (ς ΊΟ 2 69.96 3.11 18.30 (c = ") 1260 (-0-) VI 7- 1170 (-5О _С )

-Where K = - | -CH ₂ З & о -СК

Polymers based on tetranitriles of aromatic tetracarboxylic acids and aromatic di-o-cyanamines are superior to polyhexazocyclans in hydrolytic stability. So, if the inventive polymers do not change their properties when boiling for 15 min in 10% hydrochloric acid solution, then polyhexazocyclans under similar conditions are almost completely destructuring. This allows you to significantly extend the performance of products from macroheterocyclic polymers in aggressive environments.

Claims (2)

Claim 1. Nitrogen-containing polymers of the formula 35 40 45 one_ 50 η - 10-30 as a binder for fiberglass " 2. A method of producing polymers according to claim 1 by the polycondensation of tetranitrile aromatic tetracarboxylic acid and aromatic di-o-cyanamine, taken in a molar ratio of 1: 2, in phenol in the presence of lithium chloride as a catalyst at 170180 C,