SU1207122A1 - Polymerizing oligomide and method of its production - Google Patents

Abstract

1. Polymerization oligoimide based on a phosphorus-containing bis-furan compound and a metaphenylene bis-maleimide of the formula N-Ar (L -N. CH, -OOC-CH-CH2COO l I (OCH3) 2 iN-Ar-ia where n 1 -4, with enhanced flame retardancy 2. Method for producing polymerization of V-capable oligoimide by condensation of meta-phenylene bis-maleimide with bis-furan compound in aproton-OHCHOOC-CHO-CH-CH-COO-CHP o I (OCH) solvent 2 when heated characterized in that, in order to increase the fire resistance of the oligoimide, as a bis-furan compound, The user him fosfrrorgani- cal derivative of formula

Description

one

The invention relates to the synthesis of new chemical compounds specifically to phosphorus-containing oligomers (FON), which can be used as adhesives, coatings, press powders and bonding dp products, operated in an environment with a high oxygen content.

7

i 1222

The aim of the invention is to impart to polymerization capable oligomers properties that provide enhanced fire resistance to materials made from them,

Polymerization-capable oligomers are obtained by the interaction of a phosphorus-containing bis-furan compound.

Y-ns

 OOS-CH -CH-SOOSNgDJ) R- (ONz) 2

0

with meta-phenylene-bis-maleimide (MFBI)

Excess bis-maleimide is a prerequisite for the preparation of oligomers with terminal polymerization groups.

The change in the ratio of bis-maleimide phosphorus-containing bis-furan compound allows the molecular weight of the background to be adjusted from 1500 (molar ratio 3: 2) to 3500 (6: 5).

The reaction is carried out at 100-110 ° C in the medium of aprotic solvents - dimethylformamide (DMF), dimethyl acetamide or dimethyl sulfoxide, preferably in DMF, in which highly concentrated solutions of the starting compounds can be obtained. These solvents also dissolve the final products well. In addition, carrying out the reaction in the indicated solvents allows the reaction solutions to be used directly for impregnation of various fabrics (glass cloth, asbestos cloth, etc.). The final product of the FOI is separated by precipitating into a low-boiling solvent: methanol, acetone, isopropyl or ethyl alcohol. alcohols, chlorinated hydrocarbons, tetrahydrofuran. .

The obtained BACKGROUND is used in the form of 30-50% solutions in dimethylformamide as binders for reinforced plastics. Said oligon —CH — COOCHHDJ) R- (ONz3) 2

15

20

- 25

d: go

Zh-40 45. 50 55

Imides soften at 80-100 ° C and flow at low pressures (10-20 kg / cm). Curing of FOI is carried out at 160-180 ° C for 40- 60 minutes. These processes are not accompanied by the release of volatile products. Monolithic products are obtained by the method of hot pressing.

EXAMPLE 1 35 g of MFBI and 42 g of phosphorus-containing bis-furan compound (molar ratio 6: 5) are dissolved in 100 g of dimethylformamide. The reaction mixture is heated for 6 hours with vigorous stirring under an argon atmosphere. The cooled solution is drunk in 2 liters of methyl alcohol. The precipitate is filtered off, washed with 0.5 l of methyl alcohol and dried at 25–40 s under vacuum. 0.1-1 mm Hg The yield of the BACKGROUND is 67.2 g (80%).

Mol.m. - 3540 (). The sample obtained is cured at 180 ° C and a pressure of 30 kg / cm for 60 minutes.

The oxygen index of the cured sample is 62.0.

Found,%: C 54.2; H 4.01; N 4.74; P 3.02.

Calculated for link,%: C 55.6i H 4.04; N 4.75; P 3.1.

Example2. 8g MPIBI and 9.21 g of phosphorus-containing bis-furan compound (molar ratio 5: 4) are dissolved in 20 ml of dimethylformamide. The reaction mixture is heated at 100 ° C. for 6 hours with vigorous stirring under an argon atmosphere. The cooled solution is poured into 0.5 l of isopropyl alcohol. The precipitate is filtered off, washed with 0.1 l of isopropyl alcohol and dried in a vacuum of 0.1-1 mm Hg. to constant mass. The yield is 14.2 g (81%).

312

Mol.m., 2880 (). Curing is carried out analogously to example 1.

The oxygen index of the cured samples is 61.7.

Found,%: C 55.2; H 4.00; N 4.83; P 3.01.

Calculated for link,%: C 55.8; H 4.02; N 4.85; P 3.02.

Froze 12 g of IPBI and 12.96 g of phosphorus-containing bis-furanovoro compound (molar ratio 4: 3) are dissolved in 25 ml of dimethylformamide. The conditions for synthesis and isolation of FOI are similar to Example 2. The yield is 20.21 g (81%);

Mol m. 2230 ().

The oxygen index of the cured sample is 61.5.

Found,%: C 55.8; H 3.97; N 5.0; P 2.99.

Calculated for link,%: C 56.0; And 3.99; N 5.02; P 3.01.

Example 4. 16.5 g of IPBI and 15.84 g of phosphorus-containing bis-furan compound (molar ratio 3: 2) are dissolved in 35 ml of dimethylformamide. The synthesis conditions are the same as in Example 1. The cooled solution is poured into 0.7 liters of methyl alcohol, this is washed with 0.15 liters of methyl alcohol and dried in a vacuum of 0.1-1 mm Hg to constant weight. The yield is 25.8 g (79.8%). Mol.m. 1570

(item 1).

Oxygen cured index

sample 61.

Found,%: C 56.2; H 3.90; N 5.29; P 2.91.

Calculated for link,%: C 56.3; H 3.93-, N 5.33; P 2.95.

The table shows the properties of the image of 40 in spatial-network polymers. Polymers from POI are characterized by excellent heat resistance and physicomechanical properties. However, these oligoimides have significant

compared with the properties of 45 sufficiency - relatively low polymerization oligrimides with fire resistance, which makes them difficult (POI) (curing mode: t 180 ° C, use in an environment with increased 60, P - 30 kg / cm) . Physicochemical oxygen content.

1570 2230 2880 3540 61 61.5 64.7 62

The indicators are determined on the Instron uni versal tensile testing machine at a loading rate of 0.5 cm / min and

temperature of 20 s. The flammability of the samples was evaluated in terms of the oxygen index (GOST 21793 76) and the flame propagation velocity at the oxygen concentration in the environment.

61-62%. The smoke-forming ability of the samples is determined by the maximum specific optical density of smoke per unit mass loss of about. the sample is in the pyrolysis decomposition mode, as the most dangerous day of such systems, and the potential toxicity is in terms of the CO content in volatile decomposition products at a temperature and a 30-minute exposure. ;

The yield of carbonated residue (coke number) at 800 ° C was also recorded. Thermal-oxidative stability was estimated by the mass loss when heated at a rate of 6 ° / min.

on the device Derivatograf OD-102. The molecular weights were determined by measuring the integral heat of condensation on an ITEC-2 instrument.

Closest to the FOI on the system "

application and use are PORs obtained by the condensation of meta-phenylene-bis-maleimide with N, N-bis-furfurylidene diaminodiphenyl ether in a solution of amide solvents at 20150 ° C in the presence of a radical

hydroquinone inhibitor. POIs have good solubility in organic solvents and are capable of transition without isolation of volatile products.

in spatial net polymers. Polymers from POI are characterized by good heat resistance and physico-mechanical properties. However, these oligoimides have a significant drawback — a relatively low fire resistance, which makes them difficult to use in an environment with a high oxygen content.

3500 42.5

oh

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1800

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1800

80-90 80-90

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1850

90-100

160-180 160-180 160-180

Editor P. Gor'kova

Compiled by K. Voloshchuk

Tehred V. KadarKorrektor I.Musk

. Order 3984/1

Circulation 437Subscribe

VNIIPI USSR State Committee on Inventions and Discoveries 113035, Moscow,) K-35, 4/5 Raushsk nab.

Production and printing company, Uzhgorod, st. Project, 4

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nineteen

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1850

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90-100

90-100

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160-180

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Claims (2)

1. A polymerization oligoimide based on a phosphorus-containing bis-furan compound and a metaphenylene bis-maleimide of the formula with _x • Ν-ΑΓ H ₂ COOH ₂ C-HC-COOH ₂ C co ' D = (P (OCH _{3) 2.} Sn.-CCA-CH-CH _z COO-CH ₂ L, 'ι O = P (OCH ₃ ) ₂ where η = 1-4, which has increased fire resistance. 2. A method for producing polymerization of a capable oligoimide by condensation of meta-phenylene bis maleimide with a bisfuran compound in an aprotic solvent under heating, characterized in that, in order to increase the fire resistance of oligoimide, an organophosphorus derivative is used as its bis-furan compound formulas SU. „> 1207122 СНоООС- СН / -СН-ООО- he ^ά I O = P (OCH ₃ ) ₂