SU770101A1 - Oligophenyls for producing heat-resistant polymeric materials - Google Patents

Description

(54) OLIGOPHEINE FOR MANUFACTURING

HEAT-RESISTANT POLYMER MATERIALS

one

This invention relates to novel chyltic compounds, specifically oligophenylene, used to produce heat-resistant structural materials.

Oligophenylenes are known for producing heat-resistant structural materials obtained by polycyclocondensation of acetyl aromatic compounds and their ketals {1.

The resulting fusible and. soluble aorpopimers have terminal acetyl and ketal groups capable of entering into further condensation with the formation of a three-dimensional cross-linked structure. However, hardened polymers have high thermal and heat resistance. only when the structuring of the prepolymers is carried out at 450 ° C, which complicates the processing of polymers into products. The structuring reaction is accompanied by the release of low molecular weight compounds, which degrades the quality of products made from such polymers.

The chain of the invention is to provide oligsphenylene properties that prevent the release of low molecular weight products during their structuring. These properties are determined by the ion structure of oligophenylene oligophenyls of the general formula

1 / JJU

where R is a radical of the formula.

 Ar - radicals of the formula

- ILM -F () V J / with reduced viscosity, measured at 25 ° C in chloroform, 0.05-0.2 dl / g. Oligophenylenes of the aforementioned general formula are obtained by polycyclocondensation of ketals of diacetylaromatic compounds of the general formula Shz (C2H50) gC-Ar-, C (OC2H5) 2SHe, with the ketal of mio-acetylromatron compounds of the general formula PS (OC2I5) 2SH, where F), F, -fromicosomalomatics, of the general formula 15–25 ° C in the catalyst’s history — dry hydrogen chloride, followed by the introduction into the reaction of a 4–8 fold molar excess of ketal acetophenoia or 2-astilbifeyylene in order to obtain preformers that do not contain horseradium catalytic rpyim. . The structure of the oligophenylene obtained in this way was confirmed by IR spectroscopy data. In the spectra of oligophenyenes, there are bands in the region of 740 and 832, indicating the presence of biphenylene fragments, noJrocbi "o6jracTH 882 and 1400, and 4amijuic 1,3,5-trisamendine benzene benzam, corresponding to 1,4-) area of 818 and 1525, corresponding to 1,4-) XI is substituted with P) GM benzene dram and bands in the region 700 and 760, corresponding to monosubstituted benzene dram. Oligophenylene is soluble in aromatic and chlorinated hydrocarbons and poorly in alcohols and acetone. Their melting point, depending on the structure and molecular weight, lies in the range from 120 to 200 ° C. The reduced viscosity determined at 25 ° C in chloroform (C 0.5 dl / g) is 0.050.2 dl / g. Spruce of the hofenylene is structurized directly in the manufacture of the product by hot pressing at 360-380 ° C. The use of curing catalysts (monovalent rhodium compounds (such as) CCl and norbornodienylchloride (rhodium dimer)) reduces the structuring temperature to 270-280 ° C. Examples of tetrahydrochloride equipped with a broom, a dropping funnel and a bubbler, 0.465 g (1.5 mmol) of THIS OT10 KETAL p-diacetyl bembol, 0.577 g (1.5 mmol) of ethyl ketal 2,6-diacetyl are charged. biphenylene, 0.58 g (0.57 ml, 3 mmol) of acetophenone ethyl ketal and 9 ml of absolute benzene. The permutation is turned on and after the components have dissolved, the current of dry HCI (volume flow 1014) is started to flow. After the end of the induction period, 5-6 ml (25-30 mmol) of ketal acetophenoia are added from the dropping funnel, in portions of 1.5-2 ml with an interval of 10 -5 minutes. After adding the last portion, the mixture is saturated with HCI for 30 minutes, stirring up and passing through of HCI is turned on, and the reaction mixture is left to stand at 15-25 ° C for 36- 48 hours. After that, the mixture is filtered and poured with stirring in 80-100 ml ethyl alcohol. The polymer obtained is thoroughly washed with hot alcohol, 5% solution of NaHCO3, water until neutral, and washing under and again. alcohol, then vacuum at 60 ° C to constant weight. Obtain 1.2 g oligophenlei-yellow color, the properties of which are in the table. 1. Example 2. Oligofeyilen (prepolymer) prepared according to Example 1 is heated in a condensation tube at 380 ° C without a catalyst or at 280 ° C with 10 wt.% In argon for 4 hours. . The results of dynamic TGA on structured polymer air are presented in Table. I. PRI me R 3. The prepolymer prepared in Example 1 is pressed at 380 ° C without a catalyst or at 280 ° C with 10 pes.% D for 1 hour at a specific pressure of 600 kg / cm. A black polymer sample is obtained, the properties of which are given in table. 1. EXAMPLE 4. According to the method described in Example 1, other prepolymers based on ketal of 2,6-diacetylbifele and ketals of diacetylromatic compounds of the general formula CH3 (C2HsO) jAr- (OC2Hs) 2CH3 are obtained. where Ar has the above values w. Properties of the prepolymers and the properties of structured polymers are given in table. 1. PRI me R J. A four-necked flask with a bane dish, a dropping funnel and a bubbler., Is charged with 0.93 g (3 mmol) of ketal p-diacetylbenzene, 0.805 g (3 mmol) of ketal 2-acetylbif.tlena and 9 ml of absolute benzene. Further operations are performed as described in Example 1. 1.1 g of a yellow-colored polymer soluble in aromatic and chlorinated hydrocarbons are obtained. The properties of this and obtained similarly to forpstilimers on the basis of ketal 2-acetylbiphenylene and ketals of diacetyl aromatics are listed in Table. 2. Structuring prepolymers results in crosslinked products, whose properties are listed in the table. 2

5,770) 01 "

As shown in the tables, the resulting oligo release of low molecular weight substances) npeiphenylenes, after curing, is relatively diluted into polymers with high thermally stable miBKHX temperatures (which prevents them from).

Properties 4n) rp (); | imriv and octane polymers based on 2,6-dhacetylbnphenylene lilac lines and ketals and isomethyl aromatics of the general formula

cHHCjHjO. .: - Ah - s (os, n,), sn,

Table I

I -. at -1M) C without K Ti: miatnpa at - "rwpjKflwoiipn; sOCi-lOBtc..l fttilPPtijirci Properties of the pre-polygame m C (of the polymers based on the purple ketela daadyl arrythylaciones of the general formula of a general formula with a general formula of yellow heart). -Ag-S (OS, H,), CH,. Ketvl 2-11 "11bifenshe" a

0.09150-160 1 450500550I.

at 4304 ") 5002 170-180 440 11.-:. in w ... oh .. I - otmrzhpeno with W (fC wee katal tor, in - with ZKOS "10 Mc.lf RhlPPhjIiCI

24

250

18,160

200 1EO

1W

Claims (1)

in terms of iwiuMMtecxoro TGA in air, according to other tests, PP-1 plastometer with a load of 300 kg / cm 520.314ua. ipvmicheskogo TGA bipyu оч ochu and in a crumbled slime mctom (tre PP-1 with an implant of 200 kg / cm) Invention Oligophenylenes of the general formula At V- where R - radicals of formula Ar - radicals of formulas with reduced bone, measured at 25 ° C in chloroform, 0.05-0.2 dp / g to obtain heat-resistant polymeric materials. Information taken into account during the examination 1. USSR author's certificate No. 302022, cl. 08 G 61/10, 1971 (prototype) .