3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate

Pale yellow to colorless transparent liquid

Liquid

mixer, Reflux condenser, In a flask equipped with a stirrer, 12 parts of water was added while purging with nitrogen, 0.38 parts of 12-tungstophosphoric acid, 0.56 parts of phosphoric acid, Sodium carbonate was added, The pH was adjusted to 5.0.Further, 0.6 part of trioctylmethylammonium acetate (xylene solution of trioctylmethylammonium acetate manufactured by Lion Akzo) was added, After refining the tungstic acid type catalyst, 35 parts of toluene was added and dissolved, As a two-layer system solution, The mixture was stirred vigorously at room temperature for 1 hour.Here, equation (1).And 22 parts of the compound represented by the formulaThe solution was heated to 50 ° C., While stirring, 24.8 parts of 30percent by weight hydrogen peroxide water was added, The mixture was further stirred at 50 ° C. for 15 hours as a postreaction.After cooling to room temperature, 1 part of 30percent by weight sodium hydroxide aqueous solution, 10 parts of 20percent by weight aqueous sodium thiosulfate solution was added and stirred for 1 hour, After 15 parts of toluene was further added, It was left standing.after that, The organic layer separated into two layers was taken out.To the obtained organic layer, 8.8 parts of Hokuetsu HS (phenol · formaldehyde resin beads manufactured by Ajinomoto Fine-Techno Co., Ltd.) which had been washed with methanol in advance was added, The mixture was stirred at room temperature for 2 hours and filtered under reduced pressure.The resulting solution was washed three times with 30 parts of water, Using a rotary evaporator, By distilling off the organic solvent, 20 parts of a desired epoxy compound (EP1) was obtained.The obtained epoxy compound was pale yellow, Epoxy equivalent is 130 g / eq. , And the viscosity was 241 mPa · s.The amount of remaining quaternary ammonium salt (gas chromatography) was 50 ppm, The residual tungsten content (ashing method) was 1 ppm.The obtained epoxy compound contained 6percent monoepoxy compound, 93percent diepoxy compound, It is 1percent water adduct, Main purity measurement by GPC showed 99percent.Examples 2 to 5The reactions were carried out in the same manner as in by changing the reaction conditions (liquid composition), and the results are shown in Table 1 together with the results of Example 1. Incidentally, in Example 5, a substrate different from that of was used, but the concentration of the substrate was the same as in Example 1, i.e., 0.448 mol. In Example 4 using benzonitrile as the nitrile compound, the conversion ratio was higher compared with other Examples using acetonitrile and the reactivity was good. In Example 5, the conversion ratio was lower compared with employing the same synthesis conditions, and the product was monoepoxide only. It was revealed that the reaction selectively occurs with the double bond of the cyclohexene skeleton.In a eggplant flask having a volume of 100 ml, 2.52 g (10.0 mmol) of 3 ', 4'-epoxycyclohexylmethyl 3, 4-epoxycyclohexane carboxylate, Methacrylic anhydride3.70 g (24.0 mmol), Monobenzyltrimethylammonium chloride0.93 g (0.5 mmol)And 4-methoxyphenol12.4 mg (0.1 mmol) were charged, And the mixture was stirred at 100 C. for 24 hours.Subsequently, the reaction solution was concentrated, and the obtained concentrate was treated with silica gel column chromatography (ethyl acetate / hexane = 1/1 (v / v)), 4.54 g of a colorless liquid (purified product) was obtained (yield 81.0%).The epoxy compound and a curing catalyst were blended according to Table 3 and applied to an aluminum plate (A1050P) whose film thickness was brought up to 15 mum, followed by curing by irradiation with the dose of 175 mJ/cm2. The property of the film surface immediately after irradiation; the property of the film surface after 1 minute o: Cured, Delta: Cured only in the surface × : Not cured with tack Pencil hardness: evaluated according to JIS K5400. Table 3 Applicatio n Example 7 Application Example 8 Application Comparative Application Example 3 Comparative Application Example 4 Epoxy resin obtained in 100 Epoxy resin obtained in Example 3 100 Epoxy resin obtained in Comparative 100 CEL-2021P 100 YD-128 100 UVACURE1591 3 3 3 3 3 FC430 0.5 0.5 0.5 0.5 0.5 Property of film surface immediately after irradiation omicron omicron Delta × × Property of film surface after one minute o o o o × Pencil hardness after 20 min. (scratch) 2H 2H HB HB not curedCEL-2021P: 3, 4-epoxycyclohexenylmethyl-3', 4'-epolxycyclohexyenyl carboxylate manufactured by Daicel Chemical Industries, Ltd. YD-128: Bisphenol A-type epoxy resin (Manufactured by Toto Chemical Corporation, epoxy equivalent = 190, Viscosity = 13, 600 mPa·s/25C) UVACURE 1591: sulfoniuim Salt-based photo cationic polymerization initiator, manufactured by Daicel UCB, Industries, Ltd. FC430: Leveling agent, manufactured by 3M, CO., Ltd.A sample of 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate of epoxide content 7.7 mol/kg (87.4 g) and Boltorn H40 (12.6 g) were heated together at 100 C. under vacuum for ½ hour. The mixture was allowed to cool to 60 C. and then Amberlyst (TM) 15 ion exchange resin (31.5 g) is added. This mixture was heated under vacuum at 150 C. for 4 hours by which time the epoxy value had fallen to 5.3 mol/kg. The reaction mixture was allowed to cool and the catalyst removed by filtration.A sample of 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate of epoxide content 7.7 mol/kg (87.4 g) and Boltorn H40 (12.6 g) were heated together at 100 C. under vacuum for ½ hour. The mixture was allowed to cool to 60 C., and then the filtered but unwashed catalyst (70% Amberlyst (TM) 15 ion exchange resin) from above example 13a (44.7 g) is added. This mixture was heated under vacuum at 150 C. for 7 hours by which time the epoxy value had fallen to 5.6 mol/kg. The reaction mixture was allowed to cool and the catalyst removed by filtrationA sample of 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate of epoxide content 7.3 mol/kg (88.0 g) and Boltorn (TM) H30 (12.0 g) are heated together at 100 C. under vacuum for ½ hour. The mixture is allowed to cool to 60 C. and then Amberlyst (TM) 15 ion exchange resin (30 g) added. This mixture is heated under vacuum at 150 C. for 6 hours by which time the epoxy value has fallen to 5.4 mol/kg. The reaction mixture is allowed to cool and the catalyst removed by filtration.

Intermediate of epoxy resin; coating of food packaging materials; can be used for light modeling and making medical models; intermediate of electronic materials; automotive primer; high-voltage cable

Intermediates

100,000 - 500,000 lb|(1979) NO EVIDENCE OF COMMERCIAL PRODN IN U.S.|(1981) NO EVIDENCE OF COMMERCIAL PRODN IN U.S.

Molecular Weight:252.31
XLogP3:1.5
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:4
Exact Mass:252.13615911
Monoisotopic Mass:252.13615911
Topological Polar Surface Area:51.4
Heavy Atom Count:18
Complexity:356
Undefined Atom Stereocenter Count:6
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes