SU626098A1 - Method of producing olgomethylendiphenyloxides - Google Patents

Description

one

The invention relates to the field of thermosetting polymers, in particular, to the preparation of stable oligomethyl deciphenyloxides, which are the basis for electrical insulating varnishes.

A known method for producing o (1) () metlone diphepyloxy by reacting dphenyl ufir with formaldehyde in the presence of acid catalysts 1. The polymers obtained on their basis are unstable (precipitates), which makes it difficult to use them as electrical insulation materials.

It is also known that thermosetting resins on oenovo oligomers obtained by condensation of 2diphenyl ether with formal1) dehydrate in the presence of aromatic acids or amine offenses of the formula

X

Y

where X is NG; HE;

Y —NHa; SOOP; N.

But the product obtained by this method, due to the presence of carboxyl, amipoproxrunn, is capable of curing at a temperature of 200 ° C for 9-12 mpn.

In addition to the proposed technical solution is the method of obtaining oligomethylenphenyl oxide and thermoreactive polymers on their basis,

the interaction of difenplating ester and formaldehyde in the presence of cepHoii acid at a temperature of 80-90 ° C with the next condensation of the H and a preparation oligomer in the presence of the Friedel Crafts catalyst in polymer 3.

However, the resulting liquid ol1 homer is unstable, and a precipitate forms during the process of snoring 1, the amount of which increases during the course of time. Sediment formation is also observed in lacquers that are not pa-based.

In order to increase the stability of oligomethylenediphenyloxides in the proposed method, obtaining vedhts in the presence of diarplmethaaa. ditholi.h- or dicumplmetaia, taken in an amount of 0.1 - 1 mol and 1 mol of dphenyl ether.

The first oligomers are stable. Chemical analysis data

And it is proved that the NPP is stored for 180 ° C at a temperature of from +5 to + 30 ° C, the content of ethoxyl groups, hydroxyl groups and active oxygen remains pepmenmen; no precipitation is observed during the same period,

The oligomers are stored as a uniform viscous liquid.

In Tabdins nrivdsio, a comparison of svOKT) oligomers OB obtained from but known sioosu 3 -rimer 2, i.e., without diarylmethane, and obtained by the proposed method, with dnarylmethane.

The polymers, which are based on these oligomers, have the following properties.

Specific volumetric concentration, ohm-cm: IR and 250 ° C6.8Uz

after being in an atmosphere with a relative humidity of 95zfc2% for 24 h, irn 20 ±: 2 С5.0-iOs

Electric strength, kV / ml1: iri

after staying in

atmosphere with an humidity of 95 ± 2% for 24 hours and a temperature of 20 ± 2 ° С100

Tsempt11r kzhi1 ability. AND:

in the initial state 297

at a temperature of 180С207

Oil resistance, MB more than 140

These iolimers have good adhesion.

The above irimers illustrate the implementation of the proposed method.

Example 1. In the reactor, eabzheiny mixer, reflux condenser n thermometer, iomesh, ayut 306 weight. including (1.8 mol) difeiochova ether, 39.2 weight. including (0.2 mol) ditolylmethian n 150 weight. including (5 mol) and aaraform. Into the mixture, a preliminarily prepared solution was introduced. 224 wt. hours (2.3 mol) of concentrated seric acid in 344 weight. h (7.5 mol) of ethyl alcohol. The reaction mixture is heated to 80-90 ° C and the temperature is maintained for 3-10 hours for 8-10 hours, then 1000 everything is introduced into the reactor. including toluene and 250 wt. including butyl alcohol.

The resulting solution is washed with water until neutral and the toluene is distilled off.

and butyl diri residual pressure 50-100 mm Hg. Art. At the same time, 500 wt. including (91.1% of theoretical yield) of olgomethylene diphenyloxide. Functional weight in oligomer:

ethoxyl groups 11.77%; hydroxyl groups 0.25%, active oxygen 1.13%, molecular weight 340.

Example 2. In the reactor, in the reactor

nrnmere 1, iomesh ayut 238 weight. including (1.4 mol) dipheyl ether, 117 weight. including (0.6 mol) dicumilmetaia n 150 weight. including (5 mol) and aaraform. A preliminary solution is introduced into the mixture obtained.

224 weight. h (2.3 mol) koiseptrirovannuyu series of kit.choty in 344 weight. h (7.5 mol) of this. alcohol.

The reaction is carried out under conditions analogous to those described in Example 1. This gives 450 weight. including (, 93% of theoretical yield) olgomethylnphenyl oxide. The content of functional groups in the oligomer: ethogenic primers 10.70%, hydroxyl jpynn 0.22%, actinocyloric acid 1.10%,

molecular weight 395.

Example 3. In the reactor, opnsanyy in nrimer 1, is prevented by 170 weight. including (1 mol) difennlovogo efnra, 196 all. including (1 mol) of ditolylmethane and 150 weight. including (5 mol) and aaraform. A solution of 224 wt. Is injected into the mixture. h (2.3 mol) of concentrated sulfuric acid in 344 all. h (7.5 mol) of ethyl eiprt. The reaction is carried out under conditions similar to those described in Example 1. 370% is obtained. h. (65% of the theoretical yield) of oligomethylenedifeiiokspd with a functional composition: ethoxy groups of 11.3%, hydroxyl groups of 0.24%, active oxygen of 1.50%, molecular weight 340.

The oligomers prepared in Examples 1 to 3 are brown viscous liquids that are well miscible with aromatic hydrocarbons and acetone.

Claims (3)

1.Die makromol Chem., 97, 9. p. 163-173. 2. Authors certificate of USSR L 403533, cl. From 08G 7/00, 1969. 3. The author's certificate of the USSR. YO 377318, cl. From 08G 7/00, 1971.