SU649718A1 - Cycloaliphatic epoximides as monomers for obtaining heat-resistant polymer materials - Google Patents

Description

1,1-bys- (hydroxymethyl) -cyclohexen-3 diglycidyl esters or tetrahydrophthalic acids.

Cycloaliphatic epoxyimides are solids with m.p. 50-70 ° C, readily soluble in common solvents, which is important and their use as components of bonding), their for reinforced elastics. These compounds can be processed into polymers without modifying additives and active diluents.

The polymers obtained by curing the cycloaliphatic epoxy imides of formula (II) with anhydride hardeners have high heat resistance and the temperature of the onset of destruction, as well as a higher limit of the degree of irregularity and stretching.

Example 1. A mixture of 141 wt. including dng; tetrahydrophthalic acid cidyl ester, 151 wt. including tetrahydrophthalimide and 1.5 wt. including N, N-dimethylbenzyl-amia, heated irs to 130 ° C until glycide groups disappear completely (2-3 hours). After removal of the catalyst in vacuum, a triolefin with a melting point of m.p. 54 ° C, iodine number 129.5% and the content of hydroxyl groups 5.64%. For CsoHseOioN, an iodine number of 130.2% was calculated, a hydroxyl number of 5.82%. 292 weight. including 1,2-byc- (1-tetragpdrophthalmpo-2-hydroxypropyl) - cyclohexe-3-carboxylate is dissolved in 1000 ml of chloroform, 34.2 wt. including sodium acetate and dosed out dropwise over 1 hour 342 wt. including 40% peracetic acid, and the temperature kept at 33-35 ° C. The reaction mass is maintained at this temperature for 3 hours, after which the organic phase is separated and neutralized with anhydrous sodium carbonate. The precipitate of sodium chloride is filtered off. After evaporation of the mother liquor and vacuum drying at 120 ° C / 2 mm Hg. Art. within 3 (276 parts by weight (87%) of a light yellow solid glassy product, containing 16.4% of epoxy resin and 5.87% gproxyl).

After recrystallization of a sample of the obtained product from a mixture of petroleum ether / ethanol (2: 1), 1,2-bass-1 (3,4-eioxyhexahydrophthalimido) -2-hydroxypropyl-4, 5-epoxycyclohexane-carboxylate (product I) with t pl. 67 ° C.

Found,%: epoxy groups 19.63; hydroxy groups 5.16; C, 56.81; H 5.48; N4.12.

С:;, оНзб01з 2.

Calculated,%: epoxy groups 19.93; hydroxyl groups 5.38; C, 56.96; And 5.74; N 4.43.

Example 2. A mixture of 148 wt. including diglycidyl ether (3 (4) -methyltetrahydrophthalic acid, 165 parts by weight. 3 (4) -methyltetrahydrophthalimide and 1.6 parts by weight of triethylamine are heated at 100-110 ° C until the glycid groups disappear (2-3 hours) After removal of the catalyst, 313 parts by weight of a light yellow, viscous noncry5 steel product with an iodine number of 120.77% and a hydroxyl group content of 5.27% is obtained. Epoxidation obtained

triolefine under the conditions of example 1 leads to trieioksid (light yellow solid glassy substance) with 85-90% yield n containing 15.26% epoxy and 5.72% hydroxyl. After recrystallization from a mixture of ether and ethanol (2: 1), 1,2-bass-1- (3 (4) -methyl-4, 5-eioxyhexahydrophthalimido) -2-oxypropyl-3 (4) -methyl-4, 5 - epoxycyclohexanecarboxylate with m. Pl. 52 ° C (product 2).

 Found,%: epoxy groups 18.38; hydroxyl groups 5.17; C, 58.45; H 6.34; N 3.97.

SzzN42O1zM2

Calculated,%: epoxy groups

18.69: hydroxyl groups 5.04; C, 58.75; H 6.27; N 4.15.

Example 3. A mixture of 127 wt. including diglycidyl ether 1,1-bis (hydroxymethyl) -cyclohexa-3 151 weight. including tetrahydrophthalimide to 1.4 wt. h. M, M-dimethylbenzylamine is heated at 130 ° C until the glycide groups disappear (2-3 (). After removal of the catalyst, 278 parts of light yellow, viscous and crystallizing product is obtained at a comiat temperature. T 37 ° C, iodine number -L 136.2%, hydroxyl number 5.90%. For C3oH4oO8N2,%: iodine number 136.79; hydroxyl number 6.11.

By epoxidizing the obtained -l-6uc- (tetrahydrophthalimido-2-hydroxypropyl) oxymethylcyclohexene - 3 in the words of irimer 1, you get a solid glassy product in 90-95% yield. Content%: epoxy groups 16.73; hydroxyl groups 6,34. After recrystallization from methanol, 1,1-b "c- 1- (3,4 - epoxyhexahydrophthalimido) -2-hydroxypropyl - oxymethyl-3,4 - eioxy0 cyclohexane (product 3) with m.p. 49 ° C. Found,%: epoxy groups 20.64; hydroxyl groups 5.78; C, 59.12; H 6.50; N 4.42.

C3oH4oOjiN2

5 Calculated,%: epoxy groups 20.86: hpdroksilny groups 5,63: C 59,59; H 6.67: N 4.63.

Example 4. Of the 127 weight. including diglycidyl zfpoa 1,1-bns (o1ssimegpl) -cyclohec0 sspa-3, 165 weight. Part 3 (4) -methyltetrahydrophthalimide and 1.5 wt. including triethylamine in conditions1:. example 2, get 292 weight. h. trio.chsfpna, light yellow viscous and crystallizing and distillation

5 products with an iodine number of 128.70% and so5

holding 5.44% hydroxyl rpynii. For C, J2H4408N2 is calculated,%: total number 130.2, hyaroxyl number 5.82. Epoxidation of the resulting trpolefin under the conditions of Example 1 leads to tri-epoxy in 85-90% yield. Content,%: epoxy groups 16.37, hydroxyl groups 5.94. Recrystallization from methanol gives l, l-6iic i (3,4) -methyl-4,5-epoxy-hydroxy-phthalate) -2-oxpropyl-oxpmethyl-3, 4-epoxycyclohexane (product 4) with mp of 44 ° C. Naidio,%: test groups 19.53; hydroxyl groups 5.56; C, 60.21; H 7.17; N 4.25.

C32H "O ,, N2

Calculated,%: epoxy groups 19,23; gprodigyl groups 5.38; C, 60.75; H 7.01; N 4.43.

The structure of the obtained compounds is confirmed by analyzing their IR spectra, which are characterized by the following absorption bands: 795 - asymmetric stretching vibrations of the epoxy cycle at the cyclohexane ring, 3450 c. - valence vibrations of the ON group, 1723 and 1780 s. - characteristic frequencies of the C imid cpc, 1720-1760 cm - absorption of the C O group in the ester group (for the compounds described in examples 1 and 2), 1000-1300 - РЯ | Describes a simple ether bond (for compounds described in examples 3 and 4).

PRI me R 5. 100 weight. including product 1 (see example 1) is heated to 70-80 ° C, the displacement of the cabin from 37.4 weight. including molten maleCBoro (.VIA) or 63.3 wt. including g / so-methyltstra g: drophthalic anhydride (isoMTGFA). The prepared compositions are poured into metal molds and cured according to the mode: 100 ° С - before gelatinization, 140 ° С - 2 h, 180 ° С - 2 h, 200 ° С - 12 /.

Example 6. 100 weight. including product 3 (see example 3) and agregut to 60-80 ° C, mixed with 38.1 weight. h. ras1: lavleiio1-o malei pl 64.5 wt. including so-methyltetrahydrophthalic anhydride and cured under the conditions of Example 5.

Example 7. 70 wt. including product 1 or 3 and 30 wt. including an aniline-feiolo-formaldehyde resin, dissolved in a sinter-acetone mixture (to obtain 60-70%; solution). T-10-80 glass fiber is impregnated with the prepared solution and dried out of the solvent at commanding 24 (.

The resulting “pre-reg is folded into a bag and pressed at a specific pressure of 5 according to the mode; 140 ° С - 10 hours, 160 ° С - 2 (, 180 ° С - 2 hours, 200 ° С - 8 /.

The properties of polymers obtained during curing with maleic anhydride of compounds of formula (II) and known compounds of formula (I) are presented in the table.

T and o l 1 pn

Known;

product

+

185 210

12SO

1700

500

Claims (1)

233 Claims of the invention Cycloaliphatic epoxyimides of general i-formula f) c .. o-cn-cn-cn, -gch j € - N1 j, 10 H. sn-ci- ™ - / Y ° - l --- j, x4x: ok / 5 15 //.sn. n - K NiliSnz, as monomers for the production of heat-resistant polymer materials. polymeric materials, Source of information taken into account during the examination: 1. USSR Author's Certificate for Application N ° 2156981, cl. C 07 D 209/48 07.15.75.