SU593432A1 - Bis-(3,4-epoxycyclohexane carboxylic esters) of adamantanediol-1,3 as monomers for synthesis of high-strength thermally stable epoxypolymers in production of glass plastic materials - Google Patents

Description

The invention relates to new chemical compounds - bis- (3,4-epoxycyclohexanecarboxylic esters) adamantanediol-1,3 - monomers for the synthesis of high-strength heat-resistant epoxy polymers.

Polymers based on cycloaliphatic epoxy compounds are known, for example, 3,4-epoxycyclohexylmethyl ether 3,4-epoxycyclohexanecarboxylic acid (UP-632), which have good strength only under short-term exposure to high temperature (200 ° C), but the heat resistance range 15 is limited by the temperature of destruction . In loaded structures, polymers cannot be used at temperatures higher than the Marten-20 su temperature resistance, therefore, the maximum working temperature of polymers based on UP – 612 and UP – 632 diepoxides is 200 ° С [1].

It is known that the introduction of the adamantane group leads to the production of hard epoxy resins with improved mechanical properties ^.

Hack, glycidyl esters of adamantane bisphenols (GEBFA) of the general Formula

form polymers with heat resistance and physico-mechanical properties at elevated temperatures higher than that of a product based on only bisphenol [2]. When this type of polymer is heated at 180 ° C for 4 hours, the strength characteristics do not change, but when heated for 20 hours at 200 ° C, significant degradation and deterioration of physical properties occur.

The aim of the invention is the creation of a new epoxy monomer with a modified structure, which provides the best strength and heat-resistant properties.

The goal is achieved by heme, that 3,4-epoxycyclohexanecarboxyl groups are introduced into the structure of oxyadamantane. Bis- (3,4-epoxycyclohexanecarboxylic eLirs) adamantanediol-1,3 of the general Formula

where R is hydrogen or methyl, monomers for the synthesis of high-strength thermo.

persistent epoxy polymers in the arbitrariness of fiberglass.

Polymers obtained on the basis of new epoxy compounds, in comparison with the known ones, for example, UP-632 11] or GEBFA [2], have the best 15 strength characteristics as at 200 ° С {tensile strength at bending ~ 3000–3200 versus 1700 kg / cm*; and at 250 ° C (tensile strength 15002000 against 300 kgf / sr ^). 20

The method of obtaining the proposed bis- (3,4-epoxycyclohexanecarboxylic ester) adamantanediol-1,3 is based on a similar method for the esterification of cyclohexene-3-carboxylic anhydrides ^ 5 acids with diols followed by epoxidation of the obtained diesters with an aqueous solution of peracetic acid (3}. \ Example 1 Bis- (3,4-epoxy. Cyclohexanecarbonate ester) adaman. Tandiol-1,3.

A mixture of 29 g (0.17 mol) of 1,3-adamantandiola and 82 g (0.35 mol) of cyclohexene anhydride-3-carboxylic acid is heated at 160-170 ^C under vacuum while distilling off formed · 35 cyclo- hexen-3- carboxylic acid. After

Found,%: C 70.10; H 7.53; epoxy number 19.8; saponification number 263 μγ · ΚΟΗ / γ; mol.weight. 408.

^from 24

Calculated,%: C 69.21; H, 7.69; epoxy number 20.6; saponification number 267 μγ · ΚΟΗ / γ; mol.weight. 416.4.

Iodine number is absent.

Example 2. Bis- (2-methyl-3,4-epoxycyclohexanedicarboxylic ether) adamantanediol-1,3.

Under the conditions of Example 1 of 33.6 g (0.2 mol) of 1,3 adamantandiola and 93 g (0.4 mol) of 2-methylcyclohexene anhydride-3-carboxylic acid was prepared diester having a saponification value of 265 (calcd for C ₂₆ H _bond 0 _L 272).

After epoxidation, 85.5 g (0.45 mol) of a 40% solution of peracetic acid give 70.8 g • (80%) of diepoxide with an epoxy number of 18.1%. The resulting gummy product was recrystallized from hexane. After drying under the conditions of example 1, 54.9 g (62%) of a yellow crystalline substance are isolated with a melting point of 31–32 ° С and an epoxy number of 18.8%, which corresponds to a content of 95.3% of the basic substance in the sample.

Found,%: C 70.66; H 7.83; epoxy number 18.8; saponification number 249 mg KOH / g; mol.weight. 438.

^S 26 ^{N / A}

Calculated,%: C 70.27; H, 8.11; epoxy number 19.7; saponification number 253 μγ · ΚΟΗ / γ; mol.weight. 444.5.

Iodine number is absent.

distillation of the calculated amount of the latter gives the corresponding adamantanediol-1,3 diester with a saponification number of 285 (calculated for C _2L OTs 291). Diester production time is

2-2.5 hours. The diester was dissolved in 200 ml of benzene and epoxidized 100 g (0.46 mol) of 35% peracetic acid solution at 35-40 ^e C. followed by holding at this temperature for 3 h. The aqueous layer was separated, and the organic washed with 10% sodium hydroxide solution to neutralize the excess peracetic acid, then with distilled water to a neutral reaction of wash water. After distillation of benzene get

58.6 g (81%) of a resinous substance with an epoxy number of 18.6%.

The resulting product was recrystallized from hexane. The isolated light yellow crystalline substance is dried in vacuum (4-6 mm Hg) at 100 ° C for 1.5–2 hours. 46.5 g (64%) of product are obtained with mp 31-32 ° C and an epoxy number of 19.8%, which corresponds to a content of 96% of the basic substance in the sample.

ODIIPI Order 10262/52

Claims (1)

Claim Bis- (3,4-epoxycyclohexanecarbo 40 new eAirs) adamantanediol 1.3 of general Formula - And where R is hydrogen or methyl, monomers 50 for the synthesis of high-strength heat-resistant epoxy polymers c. fiberglass production.