SU496292A1 - The method of producing dicyanates - Google Patents

Description

(54) METHOD FOR RECEIVING DICIANATES

The invention relates to methods of sweating cyanate, more specifically, oligomeric silicon of organic cyanate, which can be used to synthesize a highly heat-resistant element. A known method for producing dicyanates by the interaction of phenols with halocyanas in the presence of tertiary amines as an acid halide acceptor in an organic solvent. I However, the sex: ч chambered dioania ethers of the feNeules are: crystalline I substances with relatively high melting rates (72-236 ° C), which makes it difficult to further process them in Mayice. In addition, the presence of hard aromatic radicals between functional |% iaHaTHbif groups contributes to the pattern; only hard polymers are high; MI glass transition temperatures (360-410 ° I) The aim of the invention is to obtain I liquid, thermally stable dicyanates, I containing flexible siloxane units: of different lengths between xydathenyl groups, which, unlike the known ones, are easily processed due to a thin consistency. Change the length of the strong fragment between the cyanate-phenyl groups and the nature of the substituent at the silicon atom of the original moyumers, it is possible to widely vary the thermal and fsico-mi and thermal properties of polymers based on them. The cauldron goal is achieved by the fact that oligomeric organosilicon bisphenols of the general formula are: - -one O-CHa-Si-COSi OSi-CH.-O; see rk where n 1-150 at R.-R H: Hn / g 1-20 at. R KIgHgi at "1-" 2 b 5 is subjected to interaction with galosca pian at minus 2O - plus 20 ° C in, in the absence of a tertiary amine, followed by separation of the target product.

3,

organic solvent, it is advisable to use acetone, methylene chloride, chloroform, benzene, etc.

From the reaction mixture, cyanate can be isolated in one of two ways. According to j first, the reaction mass is poured. | vayu when mixing in ice water, | The halogenoid mixture of tertiary akshna is dissolved in water, and the cyanate falls out in the form of an oily liquid, which is then separated by known methods (de canthiae, etc.). In the second method, the salt of the tertiary amine is filtered, and lay down. The solvent is distilled off in a vacuum (7-8 mm Hg).

The structure of the obtained dicyvnatov was proved by elemental analysis, IR, spostra.

Example 1 Into a three-neck flask equipped with a stirrer, a dropping funnel with back pressure and a thermometer, load l7.34 g (0.016 mol) of bis- (2-hydroxybenzoxymethyl) diikamotilgendekasti-loksana in 20 ml of acetone and cool the solution before cooling. Then, 2.12 g (0.034 mol) of liquid cyanogen is added to the solution with vigorous stirring. 3.49 g (0, O34 mol) of purified triethylamine is allowed, so that the temperature of the reaction mixture does not rise above 5 C. Next, the reaction Mflkjcy is held for 1015 min at 0 ° C and poured into 500 ml of ice-water (C), after which di-, cyanateg precipitated as an oily liquid are washed several times with water until there are no traces of halogen. The product is then dried in a vacuum oven at room temperature.

The resulting cyanate is an oily, transparent liquid yellowish in color, yield 17.5 g or 94.1% of the theoretical. The structure of the obtained cyanate is proved by

.IR and NMR spectra and elemental analysis.

Found,%: C 41.79; 41.62; H 7.42; , 7.46; SI 28.68; 28.77.

 S

Calculated,%: C 41.26; H 7.22; Si 28.60.

Example 2. Under the conditions, the analogue of h. As described in Example 1, dicyanate was synthesized from 19.32 g (O, 04 mol) of bis- (2-hydroxybenzoxymethyl) hexamethyltri-1 siloxane, 9.27 g (0.087 mol) of cyanide and 16.22 g (0.087 mol). ) tributyl amine, yield 20.63 g, or 96.8% of the theoretical.

Example 3. In the same way as described in example 1, dicyanate i.-25.08 g (O, O08: mol)) of bisphenol with 40 dimethylsiloxane groups in a chain, 3 ml of chloroform, 1, 08 g (0, O17 mol) of cyanogen and 2 , 08 g (0.017 mol) of triethylamine. JEUiUHaHaT is an oily transparent yellowish liquid, yield 24.8 g or 84.7% of theoretical.

Example 4. Similarly to that described in example 1, diionate is obtained. from 28.92 (0.002 mol) of bisphenol containing 150 dimethylsiloxane groups, 35 ml of benzene, 0.44 g (0.0045 mol) of cyanogen and 0.4 g (0.0045 mol) of triethylamine, yield 29.14 g or 95 , 7% of the terrestrial.

Example 5. Under the conditions described in example 1, the dicyanate is prepared from 18. g (O, O22 mol) bis- (2-yxbeneia., Hydroxymethyl) heptamethyltriphenylpentacyloxane, 2.6 g (0.43 mol) of cyanogen and 4.55 g (0.043 mol) of triethylamine, yield 18.3 g or 90.5% of the theoretical.

Found,%: C 58.71; 58.60; H 6.13; 6.26; Si 17.90; 13,10.

4l 48Si5V2

Calculated,%: C 59.5; H 6.36; SI 17.86P p and me 6 p. Under conditions similar to those described in example 1, dicyanate is obtained from 21.71 g (0.042 mol) of bis- (aoksiboksox-1metsh1) -pentamethylphenyltrisiloxac, 9.16 g (O, 086 mol) bromine 1shan and 16, O8 g (0.086 mol) tributyl. amine, yield 22.83 g or 95.9% of theoretical.

Example 7. Similarly to that described in Example 1, dicyanol was prepared from 25.61 g (0, O08 mol) of bisphenol containing 20 methylphenylsiloxane units, 1, O5 g (O, 017 mol) chloro-cyanide, and 1.772 g (O, 017 mol) of triethylamine, ; Call (.Oa 24.82 g or 95.3% of the theoretical.

Example 8. Under the conditions of Example 1, dicyanate is prepared from 18.36 g (0, Ozmol of bis- (2-hydroxybenzoxymethyl) tetramethvdphenyltrisilone1, 4.01 g (O, 06 mol) of cyan chloride and 6.60 g (O, Ob mol a) trietaminamine, yield 18.76 g or 94% of the theoretical.

Found,%: p. 61.76; b1.75; H 5.70; 3.62; Si 13.91; 13.87,

  2

Calculated,%: C, 61.36; H 5.42; Si 13.46.

, Example 9. Under the conditions described; As described in Example 1, noJiy aioT, dioin i ester from 27.3 g (O, 01 | mol) of bisphenol,; containing a total of 10 difenvos lrksanovyh; units, 1.47 g (Oi, O2 mol) of cyan chloride and 2.42 p (0.0 mol () of triettlamine, yield 26, Q4 g or 56.6% of the theoretical.

The subject of the invention. A method for the preparation of dacyanates of the interaction of phenol with a halogen Shan in the presence of a tertiary amine in an organic solvent, characterized in that, in order to obtain liquid thermally stable dicyanates, silicon organic oligomers of the general formula are used as phenol

C // J Rf SNL

no-y T G / VOH0CH, tSi- OSi3 OSiOH, -0

TD y-. . ,

SNS

where p. -1-150 with R-K-H: n;

i ft L

l.1-20 at Rj-CHg, R2-: eHg5

l-1-10 with Rj-Rg-CgHg,, and the interaction is carried out at minus 20 | plus 2 O C.