SU1126571A1 - Chlorine-containing di- or triepoxydes as monomers for preparing epoxy polymers - Google Patents

Description

one

The present invention relates to new chlorine-containing di- or tri-epoxides as monomers for the preparation of epoxy polymers with high flammability and elevated n, c-ns, -o-rc, n ° and I oa tSe. The disadvantages are known to be comparative physicomechanical and those properties of the corresponding materials based on them. The purpose of the invention is for containing epoxy-compound properties of cf. The goal is the dos - a chlorine - containing di - or mi common form yJaI (HjC H - CHj - O - R - O, where as monomers for epoxy polymers.

11265712

heat and heat resistance values.

The closest compounds to the proposed chlorine-containing diepoxides of the general formula: Cn, -o c-L-o, (,) s, - "cio The method for preparing the proposed compounds is that hexachlorobenzene is reacted with diane diphenols ( ), phenolphthalein (FF), 4,4-dioxydiphenylsulfone (DODPS), 4,4-dioxydiphenylmethane (DODFM), hydroquinone (G), resorcin (P), dioxydiphenylfluorene (DDPPH), obtained in Situ in dimethylsulfoxide environment. Then the reaction mass is treated with epichlorohydrin at 50-80 ° C. The desired product is isolated by known methods, yield 96-98%. Example 1. In a flask equipped with a stirrer, a reflux condenser with a Dean-Stark trap and a device for introducing nitrogen, 40 g of diane (0.1752 mol), 200 ml of dimethyl sulfoxide and 60 ml of toluene are charged. The stirrer is turned on, a stream of nitrogen is supplied and, raising to a temperature up to, 14.016 g (0.3504 mol) of NaOH is added in the form of 9.92 n. solution. Under the conditions of the exothermic process, the temperature is maintained at 120-130 ° C and water is distilled off as an azeotrope of toluene-water. The temperature is then raised to 170 ° C and traces of water and toluene are distilled off. The temperature is lowered to 50 ° C and 24.24892 g (0.0876 mol) of hexachlorobenzene is added, B1 is kept at this temperature for 30 minutes and, 20.6 ml of epichlorohydrin is added to the temperature until it is added. Incubate the reaction mass at 60-70 ° C for 30 minutes, then cool to room temperature and precipitate in water. The precipitate is washed with alcohol, then with water until a negative reaction to C8-ION. Dried at 50 ° C, get 66,31 g (97%) of epoxy resin as a white powder.

NMR-13C spectroscopy data shows that the epoxy resin obtained in Example t consists of 1,4-bis (p-dioxydiphenyl propane) tetrachlorobenzene diglycidyl ether.

This is indicated by the appearance of signals at 125.04; 127.01-, 128.66 and 133, 24 ppm which correspond to the structure of the following form

O-CH, -CH - CH

  /

I o

Elemental and functional analyzes (Table 1) confirm the formation of the described product. . 15 PRI mme R 2. Synthesis is carried out similarly to example 1. 40 g (0.1732 mol) of diane, 225 ml of dimethyl sulfoxide and 75 ml of toluene are charged to the flask.

35.32 ml of 9.92 N are poured. sodium hydroxide solution (0.3504 mol), 16.3262 g (0.0585 mol) of hexachlorobenzene and ml of epichlorohydrin are added. The triglycidyl ester of 1,3,5-TpH- (h-dioxydiphenylpropane) trichlorobenzene was obtained:

 Cluster O

V

.-nn, n / a

OH-SN-SN / about

EXAMPLE 3 The method is carried out under conditions analogous to Example 1. To a solution of 150 g (0.599 mol) of 4,4-dioxydiphenylsulfone in 1400 ml of dimethyl sulfoxide and 300 ml of toluene are added 74.68 ml of 16.05 n.

(1.20 mol) of sodium hydroxide solution, 85.34 g (0.2995 mol) of hexachlorobenzene and 93.94 ml of epichlorohydrin are added. The diglycidyl ether 1, - (p-dioxydiphensh1-sulfon) of tetrachlorobeneol has the following structure:

i

HjC CHjCH2 o

0-lcH, -cH-tH ,,, / о Example4. Into the flask is charged 100 g (0.499 mol) of 4,4-dioxydiphenipmetane, 1200 ml of dimethyl sulfoxide, 200 ml of toluene. 60.9 hp of lj, 4 n is poured. (0.998 mol) of a solution of sodium hydroxide is added 71.1109 g (0.249 mol

H, C-CH-CHj-0

about

O-CHj-CH-CH,

hexachlorobenzene and 78.3 ml of epichloro. hydrin. The reaction is carried out as in Example 1. The 1,4-Bms (P-dioxydiphenylmethane) heterochlorobenzene diglycidyl ester was prepared, having the structure: EXAMPLE 5 The synthesis was carried out under conditions similar to Example 1. 200 g of the flask was charged ( 0.628 mol) phenolphthalein, 1400 ml of dimethyl sulfoxide and 300 ml of toluene. 78.29 ml of 16.05 are poured. (1.256 mol) rastHjC-CH-CH, -0 × f. f /. EXAMPLE 6 The process is carried out as in Example 1. To a solution of 106.318 (0.965 mol) of 1,4-dioEsibenzene (hydroquinone) in 1100 ml of dimethylsulfoxy, and 250 ml of toluene are poured. 120.319 ml of 16.05 n (1.93 mol) of sodium hydroxide solution, 89.46 g (0.314 mol) of hexachlorobenzene and 98.47 ml of epichlorohydrin are added. Diglycidyl ether 1, 4-5is (m-dioxydiphenylphthalein) of tetrachlorobenzene of formula 0-CHjm-cH was obtained. 0 / sodium hydroxide thief, .137.409 g (0.4825 mol) of hexachlorbene, ash and 151.34 ml of chlorohydrin are added. The obtained diglycidyl ether 1,4-Bis p-dioxybenzene) tetrachlorobenzene formula

n, ss, ss, ss, ss

O-CHj-CH-CHj

EXAMPLE 7 The reaction was carried out as in Example 1. 57.584 g (0.523 mol) of 1,3-dioxybenzene (resorcin) 600 ml of dimethyl sulfoxide and 200 ml of toluene were charged to the flask. 65.167 ml of 16.05 N are poured. (1.05 mol) of a solution of sodium hydroxide, 74.467 g (0.26 mol), hexachlorobenzene and 81.97 ml of epichlorohydrin are added.

The obtained diglycidyl ether 1,4-5is (t-dioxybenzene) tetrachlorobenzene formula

 CH-CNG-about

0-CH2-CH-CH2 Ex. under conditions similar to example 1, to a solution of 103.32 g {0.295 mol) 5s (oxyphensh1) fluorene in 1500 ml of dimethyl sulfoxide and 250 ml of toluene, 34.74 ml of 16.05 n. (0.59 mol) of sodium hydroxide solution. 42.425 g (0.148 mol) of hexachlorobenzene and 46.2 ml of epichlorohydrin are added. Diglycidyl obtained. Yfir 1,4-5is (p-dioxydiphenylfluorene) tetrachlorobenzene of the formula:

n, sdn CHl0 CH 2 - CH CH 2

According to IR spectroscopic studies, characteristic stretching vibration bands are observed for all

compounds for the aromatic core in the region of 1500 and 1600 cm% for Ag-C1 in the region of 1070 cm.

for a simple ester bond, in the region of 1210, 1175; for an epoxy group, in the region of 920, 880 cmL

In the numerator, the result is found, in the denominator - calculated.

The resins are cured with anhydride and amine hardeners for 2 hours. The time of self-extinguishing of the samples after removal of hardened 4,4-diaminodiphenyl- 53 methane from the flame is in the range of 3-13 s, I for fire resistance / GOST 21207-75 / they relate to

second category. The temperatures of 10% iteri mass according to TGA data for synthesized hardened 4,4-diaminodiphenylmethane lie in the range of 345 -. The properties of the cured proposed and known resins are presented in table 2. II265718 Some characteristics of semi-bonded compounds are listed in Table I.

Temperature loss of 2% mass

Thus, the use of cheaply expanding the assortment of di- and trivial and available industrial pro-epoxides as monomers for pala, duct - hexachlorobenzene, and also for self-extinguishing polymeric mothers of known (industrial) diphenols. In this case, the method of their preparation permits significantly cheaper and fairly simple and technologically advanced.

table 2

Claims (1)

Chlorine-containing di- or triepoxides of the general formula as monomers for the preparation of epoxy polymers.