SU842089A1 - Carborane-containing aromatic isocyanates as monomers in synthesis of thermoresistant carborane-containing polysocyanurates - Google Patents

Description

The invention relates to new chemical compounds, namely to carborane-containing aromatic isocyanates of General formula 1

OCN

C— CR X / where R

as monomers in the synthesis of heat-resistant to arborane-containing polyisocyanurates.

Known carbo-containing isocyanates flj containing an isocyanate group at the boron atom of the carborane nucleus _RC __-

6 ₁₀ HgNCO

The aim of the invention are carbo’-, wound-containing isocyanates, which can be used to obtain heat-resistant polymers with improved properties.

The goal is achieved by the new structure of compounds of General formula 1

They are white crystalline substances, readily soluble in ethers and acetone. Their structure is proved by the data of elemental analysis 5 on the content of carbon, hydrogen, boron and nitrogen and data on the determination of molecular masses (ebulioscopic method in acetone solution).

In the IR spectra, absorption bands characteristic of stretching vibrations of the group B – H, CO, and C – H carborane in the regions of 2600, 1700, 3060, and 2280 cm ^{- 1 are found} .

. Compounds of (carboranylphenyl) iso15 cyanates and (carboranylenediphenyl) diisocyanates are prepared by reacting a carborane derivative of the general formula where R where R jfVc-cR

H or - ^^ NCO

C — OR \ /

with phosgene in an aromatic hydrocarbon medium at 70-150 s with a yield of the target product of 75-90% of theory.

As solvents, benzene, toluene, chlorobenzene, m- or p-xylenes, dichlorobenzene are used.

EXAMPLE 1 A solution of 2.3 g of 1-aminophenyl-o-carborane in 50 ml chlorobenzene is saturated at 70 ° C with dry hydrogen chloride and then at 90100 ^C -fosgen passed to 5 Bani formed a clear solution (1 h). The solvent was distilled off in vacuo to give 2.0 g (80%) of (carboranylphenyl) isocyanate, m.p. 120-122 ° C (hexane). 10

Found,%: C 41.51; H 5.81; ^ 5

B 41.35; N, 5.40.

C ₉ H ₁₅ B _W NO.

Calculated,%: C 41.45, H 5.7 8;

B 41.50; N, 5.37.,

V _NC0 = 1695 and 2 28 0 cm ¹ . 20

Molecular mass (ebulioscopically in acetone solution): found 265, calculated 261.

The isocyanate number is 15.7-15.9 with a theoretical value of 16.09. 25

Example 2. Analogously to example 1 from 3.3 g of 1,2-di (aminophenyl) -o-carborane in 100 ml of JW-xylene, saturated with hydrogen chloride and then passing phosgene at 100 ° C for 30 1.5 hours get 2 7 g (75%) of 1,2-di- (iocyanatophenyl) -o-carborane, mp. 135-140 ° C (heptane + toluene).

Found,%: C 50.90; H 4.75;

B 28.72; N, 7.40.

^Η · * θ ^Β ΪΟ ^Ν 2 ° 2 · 40

Calculated,%: C 50.82; H 4.79;

B 28.62; N, 7.40.

1700 and 2280 cm ^- .

Example 3. In 40 ml of a 20% solution of phosgene in chlorobenzene at 0-5 ° C, a solution of 2.4 g of 1-aminophenyl-o-carborane in 10 ml of chlorobenzene is added. The resulting suspension is heated by passing phosgene at a speed of 10-15 cm ³ / h to 100-110 ° C ₍ then it is held at this temperature for 1 hour until the solution is completely homogenized. The system is purged with argon or dry nitrogen, the solvent is evaporated (about half) and the reaction is cooled weight to -10 ^ C. The precipitated product is filtered, washed with hexane and analyzed. The yield is 1.9 'g (75%) of the product, identical to the product from example 1,

Carborane-containing aromatic isocyanates are chemically active compounds due to the presence of isocyanate groups (NCO) in the aromatic nucleus. Such compounds are used to obtain polymers, for example, carborane-containing polyisocyanurates, which have a complex of valuable properties (according to the dynamic and isothermal TGA, they have higher thermal oxidative stability compared to conventional polyisocyanurates).

Carborane-containing polyisocyanurites obtained from carborane-containing aromatic isocyanates. can be used as heat-resistant binders for structural materials.

Claims (3)

benzene, toluene, chlorobenzene, J4- or p-xylenes, dichlorobenzene. Example 1. A solution of 2.3 g of 1-aminophenyl-o-carboran in 50 M) i of chlorobenzene is saturated with dry hydrogen chloride and then at-90-β-phosphene is passed until a clear solution is formed, (1 h). The solvent is distilled off in vacuo to give 2.0 g (80%) (carboranylphenyl) isocyanate, m.p. 120-122 ° C (hexane). Y-Ya- / OCN / Found,%: C 41.51; H 5.81; B 41.35; N 5.40. CgH .. C 41.45, H 5.78; Calculated,%; B 41.50; N 5.37. 1695 2280 cm. Molecular mass (ebulyoscopy in acetone solution): found 265, calculated 261. Isocyanate number 15.7–15.9 with a theoretical value of 16.09. Example 2. Similarly, when out of 3.3 g of 1,2-di (aminophenyl) -o-carc in 100 ml of L-xylene with saturation with hydrogen chloride and subsequent start-up of phosgene at 100 ° C for 1.5 h, 2.7 is obtained g (75%) 1,2-di - (isocyanatophenyl) -o-carboran, t 135-140C (heptane + toluene). L with С- / 1 / r-NCO Found,%: С 50.90; H 4.75; B 28.72; N 7.40. 1b aAccumulated,%: C 50.82: H 4.79; B 28.62; N 7.40. Lso 2280 cm Molecular mass (ebullioscopy in acetone solution): 3 were found, 326. The isocyanate number was 20.8, and the theoretical value was 22.4. Example 3. A solution of 2.4 g of 1-aminophenyl-o-carboran in 10 ml of chlorobenzene is poured into 40 ml of a 20% aqueous solution of phosgene in chlorobenzene at O-5C. The resulting suspension is heated by passing phosgene at a rate of 10-15 to 100-110 C. then at this temperature is kept for 1 h until the solution is completely homogenized. The system is purged with argon or dry nitrogen, the solvent is evaporated (about half) and the reaction mass is cooled to. The precipitated product is filtered, washed with hexane and analyzed. The yield of 1.9 g (75%) of the product, identical to the product from example 1,. Carboranic aromatic isocyanates are chemically active due to the presence of isocyanate groups (NCO) in the aromatic nucleus. Such compounds are used to obtain polymers, for example, carborane-containing polyisocyanurates, which have a complex of valuable properties (according to dynamic and isothermal TGA, have higher thermal-oxidative stability compared to conventional polyisocyanurates), Carborane-containing polyisocyanura, obtained on the basis of carborane-containing aromatic isocyanates. can be used as thermally resistant binders for materials of structural designation. Claims of the invention Carborane-containing aromatic isocyanates of the formula as o-kloomers in the synthesis of heat-resistant carborane-containing polyisocyanurates. Sources of information taken into account in the examination 1. TJ, Orgsnometal. Chem. 1970, 23,303.