SU789522A1 - 2-aliphatic-cycloaliphatic diepoxy compounds as diluting agents for epoxy resins - Google Patents

Description

Introduction of 20 wt.h. DEG-1 in resin ED-20 reduces the viscosity of the latter by 3-4 times, the breaking stress during bending of the compositions cured with maleic anhydride increases slightly 2. However, the heat resistance of the composition decreases from 116 to 85 ° C according to Martens. The purpose of the invention is the expansion of the range of diepoxide compounds that can be used as active diluents of epoxy resins, while simultaneously improving the thermal and physical and mechanical properties of the polymers obtained. This goal is achieved by the use of aliphatic-cycloaliphatic diepoxy compounds of general formula I, which are obtained by a known method 3 by epoxidation with a 35–45% aqueous solution of peracetic acid glycidyloxytetrahydrobenzoic acids, which are obtained, in a manner known from, 4, from the heart pattern, i.e. acids and epichlo hydrin. The diepoxides of the general formula I can be considered as structural analogs of aliphatic-cycloalphatic epoxides of the formula II from which they differ by an additional fragment, -o-CI2 in the molecule. On the other hand, the target compounds are analogs of the diglycidyl ethers of ethylene glycols, in which there is one glycide group. . X4,, c - “fO pa replaced by fragment p-f 1. These are colorless, low viscous liquids (2500 0 / 02-0.025 Pa-s), therefore they can be used as active thinners of high epoxy resins. The method is carried out as follows. Example. Preparation of glycidyloxyethyl-3, 4-epoxycyclohexanecarboxylate (diepoxide 1a). To 170 wt.h. 4 tetrahydrobenzoic acid hydroxyethyl ester in 450 ml of toluene, 4 MP of tin tetrachloride are added at 40 ° C and 92.5 wt.h. epichlorohydrin at. The reaction mixture at this temperature is kept for another three hours, cooled, after which 48 mass parts of it are added at 30 ° C. caustic soda for 1 hour. Complete the dehydrochlorination by heating the reaction mass for 1 hour and then add 500 ml of distilled water to dissolve the salt formed. The organic phase is separated and washed with distilled water until the neutral reaction of the wash water. After distilling off toluene and vacuum drying, 207.9 wt. Parts is obtained. (92%) product with an epoxy content of 17.25%. Vacuum distillation yields 173.6 wt.h. (76.8%) of pure glycidyloxyethyl tetrahydrobenzoate, b.p. 167-169 ° C / 7 mm Hg Content of epoxy groups,%: Found 18.63; le “4 Calculated 19.02. To 173.6 mass parts glycidyloxyethyl tetrahydrobenzoate in 520 ml of toluene, 15.2 mass parts are added. sodium acetate and 152 mass parts are dosed out dropwise over 1 hour. 50% of peracetic acid at ZO-ZZ C. The reaction mass is maintained at this temperature for three hours, then the organic layer is separated, neutralized with a 20% aqueous solution of sodium hydroxide and spilled with distilled water. After evaporation of toluene under reduced pressure and vacuum drying at 110 ° C / 5 mm Hg for two hours, 152.4 wt.h. (82%) light yellow product with an epoxy content of 33.7%. After vacuum distillation, 133.8 mass parts are obtained. (72%) of pure diepoxide, bp. 176-177 ° C / 7 mm Hg, Chav-C 0,0197 Pa.s; P% ° 1.4805, 1.1895; Found,%: C 59.62, H 7.85; . epoxy groups 35.33; MRjj 57.91, -16 ъ Calculated,%: C 59.49, H 7.49; epoxy groups 35.54) MRj) 58.15. PRI mme R 2. Preparation of glycidyloxyethyl-3, 4-epoxy-6-methyl-cyclohexanecarboxylate (diepoxide 16). From 184.2 wt.h. 6-methyltetrahydrobenzoic acid hydroxyethyl ester in 500 ml of toluene, 92.5 wt. epichlorohydrin, 4 ml of tin tetrachloride and 48 wt.h. caustic soda as in example 1, get 230,7 mass.h. (96%) of a product with an epoxy content of 15.07%. After vacuum distillation, 187.4 wt.h. (78%) pure glycium-. Dioxyethyl-6-methyltetrahydrobenzoate, bp 174-176 s / 7 mm Hg Content of epoxy groups,%: Found 17.23, C and H; JO O., Calculated 17.91. From 187.4 wt.h. glycidyloxyethyl-6-methyltetrahydrobenzoate in 600 ml of toluene, -1.42.2 wt.h. 50% peracetic acid and 14.2 wt.h. Sodium acetate as in Example 1 gives 175.9 mass parts (88%) of an almost colorless product with epoxy groups content of 32.12%. After vacuum distillation, 148 mass parts are obtained. (74%) of pure diepoxide, bp. 186-168 / 7 mm Hg

as: 00236 Pa-s; h "1.4848, d" 1.1748.

Found,%: with 60.49; H 7.35, epoxy groups 33.03,

MR 62.48,

) H205

v U U

Calculated,%: with 60.92; H 7.86; epoxy groups 33.59; MR 62.77.

The structure of the compounds obtained is confirmed by the analysis of their IR spectra. The spectra contain the following characteristic absorption bands: 797.812 3000 cm — deformation and, respectively, stretching vibrations of the epoxide at the cyclohexane ring, 912 cm deformation vibrations of the glycide epoxide, 1750 — stretching vibrations of the carbonyl group, 11001300 — a number of bands that characterize an ether linkage. In the spectrum there are no bands 670–1670 characteristic of double bonds in cycloalkenes, which confirms the absence of double bonds in the compounds obtained.

Froze Compounds 1a and 16, as well as 3,4-epoxyhexahydrobenzylglycidyl ether (UP-656), are cured with stoichiometric amounts of hexahydroethyl anhydride with the addition of 3 wt.h. ethylene glycol per 100 wt.h. of epoxide according to the regime of 100 C / h before gelation + 120/2 +

tl40 / 2 + 160/2 + 180/6.

The properties of the obtained polymers and the known cured hexahydrophthalic anhydride of 3,4-epoxy-6methylhexahydrobenzylglycidyl ether of the formula S are presented in Table 1.

PRI me R 4. Prepare four compositions, one of which contains 100 wt.h. ED-20 resins, the rest with - 90 mass.h. ED-20 and 10 wt.h. proposed diepoxide

. 1a or UP-656 and DEG-1 diepoxides. All compositions are cured with stoichiometric amounts of isomethyltetrahydrophthalic anhydride in the presence of 0.5 wt.h. accelerator

UP-606/2 according to the pre-gel formation mode is + 120/2 + 140/2 + 160/10.

The properties of the compositions and polymers are given in table 2.

PRI me R 5. Four compounds, 5 prepared analogously to example 4, were cured with stoichiometric amounts of 3,3-dichloro-4,4: -diaminodiphenylmethane. Curing mode 120 s / h to gelation + 140/2 + Q 460/6 + 180/2.

The properties of the compositions and polymers are given in table.3.

Table 4 shows a comparative description of the compositions and polymers based on the binder EDT-10, containing 5, wt.h: resin ED-20

100, DEG-1 20 triethanolamine-1 (TEAT-1) 20, and modified binders, in which the DEG-1 resin is replaced with an equal amount of the proposed diepoxide 16 or the UP-656 diepoxide. Curing is carried out according to the mode before gel formation + 140/4 + 180/6.

From the data table. 1 it follows that

5, the polymers obtained on the basis of the proposed compounds, diepoxides of the formula f and UP-656 practically do not differ in properties. However, in mixtures with ED-20 (Tables 2–4), the proposed compounds yield polymers /

0 characterized by increased strength and elasticity compared with the known aliphatic-cycloaliphatic diepoxides of the formula F and UE-656,

5 as well as high heat resistance and viability compared with aliphatic diepoxide. DEG-1.

Due to the high specific functionality and the presence of the cycloaliphatic epoxy group, the proposed compounds, when used as active diluents, for example, ED-20 resins, increase the viability of the composition, the heat resistance of the polymers obtained, along with the improvement of their physicomechanical properties.

Table 1

113

690 910

4.2-4.5 4.2-4.5 110

116

105

675

645

880 920 890

3.7-3.8

Heat resistance according to Martens, ° С

The viscosity of the composition according to VZ-1, Pa

Strength, kgf / cm /, .bending

when stretched

Relative extension,%

Martens heat resistance,

The viscosity of the composition according to VZ-1 at

Composition properties (,

19-2018-19 25-35

30-3430-3212-15

1000-1050 820-860 800-850

5-6

7895228

Table 2

80

95

22

36

750

720 680 660

2.0

1.9

Table3

50

80

The composition

Claims (2)

2.5-3.5 1.8-2.2 180 140 978 Claims of the invention Aliphatic-cycloaliphatic diepoxide compounds of general formula /., F. -fu o-gnggi.sn ", where R N or CH, as thinners epoxy resins. 9522 10 Sources of information taken into account during the examination 1. England patent W 111527, cl. C 07 d 1/18, published 1966. 5 2. Plastics Handbook, t. 2. M., Himi, 196.9, p. 68-70. Z. Malinovsky M.S. Olefin oxides and their derivatives. M., Goskhimizdat, 1961, p.64. | 4.Boittzer H., Porret D-, UotiSe F. Die Mairom Cliini., 1966.2., 5199.