SE188760C1 - - Google Patents

Description

Inventors: H Batzer, E Leumann, E Nikles and D Porret Priority granted from 17 November 1960 (Switzerland) The present invention relates to a process for the preparation of novel glycidyl ethers of the form —CH CH CH — R, CHCH, wherein R 1, R 2 and R 3 each represent a vac atom, a halogen atom, a hydroxyl group or a glycidoxy group - O-CH, -CH-CH 0 at least one of the radicals Rs, Rs or Rs represents a glycidoxy group.

The epoxide compounds of the invention of formula (I) can be obtained in this way, from alcohols of formula r / CH \ H— —CH CHCH RI ' ICH, II (II) IV— —CH 'CHCH — Rs' \ CHCH2 van in R, ', and R,' respectively denote a a hydrogen atom, a halogen atom, a glycidoxy group or a hydroxyl group, wherein at least one of the residues or R 3 'represents a hydroxyl group, is reacted with epihalohydrins or glycerol dihalohydrins, preferably epichlorohydrin. As alcohols of formula (I) the following can be mentioned, namely dihydroxy-tetrahydrodicyclopentadiene [tricyclo (5,2,1,02,6) -decane-3 (or 4), 8 (or 9) -diol]; Dupl. at 39 b: 22/10; 39 c: trihydroxy-tetrahydrodicyclopentadiene [tricyclo (5,2,1,02,9-decane-3,4,8 (or 9) -triol]; chloro-dihydroxy-tetrahydrodicyclopentadiene [tricyclo (5,2,1,02,6) -4 (or 3) -chloro-decane-3 (or 4), 8 (or 9) -diol]; bromo-dihydroxytetrahydrodicyclopentadiene Etricyclo (5,2,1,02,6) -4 (or 3) -bromo-decane-3 (or 4), 8 (or 9) -diol].

The reaction of the alcohol (II) with an epihalohydrin can be carried out on its own edge Mit either in one or preferably in two steps. In the one-step process, the reaction of epihalohydrin with the alcohol is carried out in the presence of alkali, preferably sodium or potassium hydride being used. In this one-step process, the epichlorohydrin intended for the reaction can be completely or partially replaced by dichlorohydrin, which, under the conditions of the process and with the corresponding alkali addition, is intermediate converted to epichlorohydrin and clarified to react with the dialcohol. In the preferred two-step process, in the first step, the alcohol (II) is condensed with an epihalohydrin in the presence of acid catalysts, e.g. boron trifluoride, to halohydrin ethers and darpa dehydrohalogenated in a second step by means of alkalis, such as potassium or sodium hydroxide, to glycidyl ether.

In the reaction of alcohols of the formula (II) with more than one hydroxyl group according to the process of the invention, constant mixtures of glycidyl ethers are obtained. In general, it has been found that the content of glycidyl ether groups is the higher the stone in which this molar ratio has been chosen.

The glycidyl ether mixtures and the glyeidyl ethers isolated therefrom are suitably characterized HRS- R, - (IN) 2— - by the content of Mycidyl groups (epoxide equivalents / kg), optionally further by the content of hydroxyl groups (hydroxyl equivalents), and by the chlorine content and determined by combustion analysis (chlorine equivalents / kg).

The epoxide group-containing ethers prepared according to the invention are thin-liquid products at room temperature. The glycidyl ether mixtures which are directly usable as such and the di- resp. the polyglycidyl ethers react with the usual hardeners for epoxide compounds and can therefore, by adding such hardeners analogously to other polyfunctional epoxide compounds, be subjected to hardening resp. bridge formation. The same harder can be used alkaline or acidic compounds. Particularly suitable have the following been found to be, namely amines or amides, such as aliphatic and aromatic primary, secondary and tertiary amines, e.g. mono-, dio and tri-butylamines, m-phenylenediamine, bis (p-aminophenyl) -methane, bis- (p-aminophenyl) -sulfone, ethylenediamine, oxyethylethylenediamine, N, N-dielyletylenediamine, tetra (oxyethyl) -diethylenetriamine, diethylenetriamine, triethylenetetramine, trimethylamine, diethylamine, triethanolamine, Mannich bases, tris (dimethylaminomethyl) -phenol, piperidine, piperazine, guanidine and guanidine derivatives, as well as phenyldiguanidine, diphenylguanidine, dicyandiamide, urea-formaldehyde-formaldehyde-formaldehyde resins , e.g. such as aliphatic polyamines and di- or trimerized oracetic fatty acids, polymeric polysulphides (thiocol), isocyanates, isothiocyanates, phosphoric acid, further polybasic carboxylic acids and their anhydrides, e.g. phthalic anhydride, methylenomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, hexachloromethylenetrahydrophthalic anhydride or endomethylenetetrahydrophthalic anhydride or mixtures thereof, further maleic or succinic anhydride, pyromic anhydride anhydride. resorcinol, hydroquinone, quinone, phenolaldehyde resins, oil-modified phenolaldehyde resins, further reaction products of Al-alcoholates resp. phenolates with tautomeric reacting compounds of the acetate ester type; Friedel-Carfts catalysts, e.g. AlCl3, SbCl1, SnCl2, FeCl3, ZnCl2BF, and their complexes with organic compounds, metal fluoroborates, e.g. zinc fluoroborate; boroxines, e.g. trimethoxyboroxine. Only monoglycidyl ethers react d.vensh. with the known harders, but in most cases during the emergence of non-bridge-forming, linear turnover products; with e.g. polybasic carboxylic acids and their anhydrides, however, they may be subjected to bridging resp. hardas. The term "hard" in the sense in which it is used means the conversion of glycidyl ethers into insoluble and infusible resins.

Of course, the curable glydeyl ethers of the invention may also be formulated with other polyepoxides, e.g. mono- or polyglycidyl ethers of mono- or polyalcohols, such as butyl alcohol, 1,4-bulandiol or glycerol, resp. of mond- or polyphenols, such as resorcinol, bis- (4-oxyphenol) -dimethylmethane or condensation products of aldehydes with phenols (novolaks), further polyglycidyl esters of polycarboxylic acids, e.g. phthalic acid, and further aminopolyepoxides, such as e.g. obtained by dehydrohalogenation of reaction products of epihalohydrins and primary or secondary amines, e.g. n-butylamine, aniline or 4,4'-di- (monomethylamino) -diphenylmethane. - The properties of Adana kanda polyepoxides can be further value-modified by the addition of monoglycidyl ethers of formula (I) as active diluents.

The glycidyl ethers according to the invention resp. mixtures thereof with harder and possibly other epoxy resins can be cured in arbitrary phase is continued with fillers, plasticizers, coloring hearths, etc. As extenders and fillers can e.g. Asphalt, bitumen, glass fibers, mica, quartz flour, cellulose, kaolin, finely divided silicic acid (AEROSIL) or metal powder are used.

The mixtures of the diepoxide compounds and hardeners according to the invention can be filled in or filled state and in solution or emulsion used as textile aids, laminating resins, varnishes, coatings, dipping resins, casting resins, extruders and putties, binders and the like resp. for the preparation of Adana agents. The new resins are particularly valuable as insulating compounds for electroinclusion.

For the above purposes, the glycidyl formed during the preparation is preferably used directly. the ether mixtures, whereby an isolation of mono-, di- and triglycidyl ethers by fractional distillation are eliminated.

In the following examples, parts denote parts by weight, percent by weight; the ratio of parts by weight to volume parts dr the same as at kilograms to liter; the temperatures are given in degrees Celsius. The epoxide levels given in epo3de equivalents / kg have been determined according to one of A. J. Durbetaki in Analytical Chemistry vol. 28, no. 12, dec. 1956, p. 2000-2001 described method with bromine cotton in glacial acetic acid.

Example 1. a) Epoxy-hydroxy-tetrahydro-dicyclopentadiene. 300 parts of 8 (or 9) -hydroxy-8,9-dihydro-dicyclopentadiene [tricyclo (5,2,1,02,6) -dek-3-en-8 (or 9) -oil, prepared on the edge of dicyclopentadiene by water storage, mixed with 1000 parts by volume of benzene. To this is added 20 parts of anhydrous sodium acetate and with stirring over the course of about 1 hour 420 parts of 42% peracetic acid. Mix the mixture by cooling at 30 °. After a further 2 hours at 30 °, the benzene solution is washed with water and the 2-n soda solution to acid-free. The solution is dried over anhydrous sodium sulfate, filtered and evaporated. Distillation of the residue gives 120'70.01 mm Hg of 3,4-epoxy-8: (or 9) - - —3 hydroxy-tetrahydro-dicyclopentadiene of the formula rCH I / H \ H— —CH I CH HC \ ICH2 I Io HO— —CH CH HC / \ CH / \ CH, / Analysis: CH1402 Calculated 0 19.25% found 0 19.45% The product contains 5.94 epoxide equivalents / kg. b) Trihydroxy-tetrahydro-dicyclopentadiene. 83 parts of 3,4-epoxy-8 (or 9) -hydroxy-tetrahydro-dicyclopentadiene are mixed with 500 parts of water and. The solution is extracted with 200 parts by volume of ether. The aqueous portion is slowly passed through a column filled with 20 g of Dowex 1-X8 * ion exchange resin (quaternization product of chloromethylated polystyrene and trimethylamine) in the form of a free base. The neutral the solution is evaporated in a water jet vacuum on a water bath. The residue is distilled in a hogya vacuum. 58 parts of 3,4,8- (or 9) -trihydroxyLetrahydro-dicyclopentadadiene [tricyclo (5,2,1,0 ") - decane-3,4,8 (or 9) -triol] with a boiling point of 2000 / 0.2 mm Hg The substance solidifies into a spray mass containing 16.5 g hydroxyl equivalents / kg (theoretical 16.3).

Triglycidyl ether. 18.4 parts of 3,4,8 (or 9) -trihydroxy-tetrahydrodicyclopentadiene are dissolved in 100 parts by volume of dry matter. dioxane. 0.4% by volume of 48% solution of boron trifluoride in ethyl ether is added and 27.8 parts of epichlorohydrin are added dropwise to the mixture during the milling at 70-80 ° over the course of 20 minutes. The solution was cooled and continued at room temperature portionwise with 12 parts of powdered sodium hydroxide. After 1 1/2 hours, filter and evaporate the solution. It is diluted with 100 parts by volume of benzene, washed with 20 parts by volume of 1-m monosodium phosphate solution, dried over anhydrous sodium sulfate, filtered and evaporated. A thin, light epoxy resin is obtained with 4.55 epoxide equivalents / kg, which consists essentially of triglycidyl ether of the formula - CH / \ H— —CHCHCH 0 CH, —CH — CH, I CH2 I CH CH CH — O — CH, —CH — CH, CHCH2 CH, - CH — CH, \ o / Example 2. a) Dihydroxy-tetrahydro-dicyclop entadiene. 328 parts of technical dicyclopentadiene dimmed [tricyclo (5,2,1,02,8) -3,4,8,9-diepoxy-decane] with formine CH \ / CH CHHC \ 0 I CH2I 0 \ CHCH HC / \ \ / CHCH2 shake in the presence of 20 g of Raney nickel and about 400 parts by volume of methanol in a water atmosphere at an initial 1000, darpa 10 and 80-120 atmospheres pressure until something irate is no longer taken up. The catalyst is filtered off and the solvent is filtered off. The residue, on high vacuum distillation, gives 240 parts of crystallized 3 (or 4), 8 (or 9) -dihydroxy-tetrahydro-dicyclopentadiene [tricyclo (5,2,1,02'6) -decane-3 (or 4), 8 (or 9) -diol] with boiling point 152-156'70.01-0.02 mm Hg.

Analysis: Gi-12602 calculated C 71.39% H 9.59% found C 71.1 Vc, H 9.5% The product contains 11.87 hydroxyl equivalents / kg (theoretical 11.89). b) Diglycidyl ether. 84 parts according to Example 2a) prepared 3 (or 4), 8 (or 9) -dihydroxy-tetrahydro-dicyclopentadiene are continued with 100 parts by volume of benzene, 200 parts by volume of chloroform and 2 parts by volume of 48% solution of boron trifluoride in ethyl ether, warming to 65 ° . Over the course of 23 minutes, 95 parts of epichlorohydrin are added dropwise. The mixture was allowed to cool to room temperature and continued to evaporate in portions with stirring over 6 minutes with 41 parts of powdered sodium hydroxide. After a further 20 minutes, the mixture is filtered, the filtrate is evaporated and heated in a high vacuum from the last residues of the solvent. The resulting thin liquid product contains 4.89 epoxide equivalents / kg and consists essentially of diglycidyl ether of the formula - - r, CH / \ H— —CHCHCH0 CIL — CH — CH, IN CHII \ 0 / —CH CH CH— —H CHCH, CH2 — CH — CH2-0— \ 0 / Example 3. a) Chloro-dihydroxy-tetrahydrodieyclopentadiene.

A flask equipped with a stirrer, condenser, thermometer and gas inlet tubes is charged with a solution of 84 parts of sodium bicarbonate in 850 parts of water and a solution of 150 parts of 8 (or 9) - hydroxy-dihydro-dicyclopentadiene [tricyclo- (5.2, - 1 , 02.6) -dek-3-en-8 (or 9) -al] 1150 parts of acetone. During good cooling and vigorous stirring, darpa is introduced between 10 and 15 ° 64 parts of gaseous chlorine. After the initial initiation of chlorine, it is determined by the edge solution (a substance sample is continued with KJ solution, surgores and the liberated iodine is titrated with sodium thiosulphate solution) that no active chlorine is present in the reaction solution.

The reaction mixture, which in a lower phase contains the reaction product with a little acetone and water and in an upper phase a saline solution with the main amount of acetone and a small reaction product, is completely freed of the water bath in vacuo from acetone, cooled and the supernatant solution. decanted. The remaining product is dried on a water bath in vacuo to give 179 parts of 4 (or 3) -chloro-3 (or 4), 8 (or 9) -dihydroxy-tetrahydrodicyclopentadiene [tricyclo- (5,2,1,02,6 ) -4 (or 3) -chlorodecane-3 (or 4), 8 (or 9) -diol] in the form of a as cold only with brownish brownish green liquid.

A sample is taken for analysis with low ether, filtered off from very small amount of end salt and re-evaporated. After this treatment, the product contains 7.2 equivalents of hydroxyl groups / kg and 18.55 percent chlorine. b) Diglycidyl ether. 178 parts of the 4 (or 3) -chloro-3 (or 4), 8 (or 9) -dihydroxytetrahydrodicyclopentadiene prepared according to Example 3a), 1100 parts of benzene are taken up, 70 ° and darph was continued dropwise with occasional cooling at 70-75 ° with 120 parts of epichlorohydrin. The mixture is stirred for a further 15 minutes and it is determined by titration of a substance sample with HBr / isatic solution that all the epichlorohydrin has been reacted. Then, at about 60 °, 145 parts of 44.2% aqueous sodium hydroxide solution were rapidly added, comparatively rising, the temperature rising to about 65 ° and the mixture being stirred for another hour at 70 °. Darpa. cooled, 100 parts of water are added to dissolve the salt and the aqueous phase is separated. The organic phase is liberated darpa hell; and the hall In vacuum from solvent and declared as hot Over some diatomaceous earth. 228 parts of a light brown comparable thin liquid product are obtained, which contain 4.54 epoxide equivalents / kg and 14.4 percent chlorine, which product consists mainly of diglycidyl ether of the formula CH, H- CH — CH2-0— —CH 1 —CH CH CH CH o CH, —CH — CH, \ 0 / CH2I CH CH- / CHCH2 \ o / Example 4. Samples of an edge at room temperature liquid polyglycidyl ether resin having an epoxide content of 5.3 epoxide equivalents / kg, which resin is prepared by reacting epichlorohydrin with bis- [4-oxyphenyl] -dimethylmethane in the presence of alkali (resin A, sample 1) and samples of triglycidyl ether (resin 13; sample 2) prepared according to Example 1c) having an epoxide content of 4.55 epamide equivalents / kg are mixed at room temperature each with 1/6 mol of triethylenetetramine per 1 equivalent of epoxide groups as curing agent. Each 100 g of the my casting resin samples was determined to determine the gel formation times and the exothermic reaction temperatures. The casting resin samples were then set at exactly 20 ° C and cast. at room temperature (° C) in aluminum cans (height 4 cm, diameter 6 cm).

The viscosities of the epoxide resins, the gel formation times and the maximum exothermic reaction temperatures have been compared with each other in the following table.

Test viscosity at 25 ° C Epoxy resin in opening hours sample minutes Gelbildhos a 100 g in 19000 2 6000 17 Maximum exothermic reaction temperature in ° C of a sample 100 g 213 18Hardat cast resin sample Mixed with blisters Blister-free The combinations according to the invention surprisingly give, despite a substantially shorter gel formation time, lower mdmal exothermic reaction temperatures.

- - An additional part of each of samples 1 and 2 was cast on glass plates in about 1110 and 1 mm layer thickness. While during paste coating of sample 1 already or briefly (2 minutes) a strong milky cloud is obtained, the paste coatings with sample 2 surprisingly remained Mara and give after curing 24 hours at room temperature flawless, hard and on the substrate excellent adhesive films, which at 1- hours of action at room temperature are resistant to 5-n sulfuric acid, 5-n sodium hydroxide solution, water, acetone and chlorobenzene.

Example 5. Samples of the polydlycid polyglycidyl ether resin having an epoxide content of 5.3 epoxide equivalents / kg (pray 1) and samples of the chlorine-containing diglycidyl ether (sample 2) prepared with an epoxide content of 4.54 epoxide equivalents / kg are melted with phallic anhydride as hardener at 120-125 °, using 0.85 equivalents of anhydride groups per 1 equivalent of epoxide groups.

Some of the cast resin samples thus obtained were cast at about 120 ° in aluminum molds (40 X 10 x 140 mm) and cured uniformly for 24 hours at 140 °.

The viscosities and properties of the polyglycidyl ether resins in the cured casting samples are given in the following table.

Polyglycidyl- Test ether resin Btijhallfastthet Slagbdjhallfast- viscosity vidkgjmin, hot in cmkg / cm2 1 9000 11,4,3 2,610.1 5.3 The combination according to the invention is excellent due to its very low viscosity at 25 ° for impregnation, laminating and casting. Similar advantageous properties are obtained, instead of 0.85 equivalents of phthalic anhydride 0.75 resp. 0.95 equivalents of phthalic anhydride per equivalent of epoxide groups, or if instead of phthalic anhydride the curing agent used is hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride or hexachloro-endomethylene-tetrahydrophthalic anhydride.

Claims (4)

Patent claim: 1. A process for the preparation of epoxide-containing compounds intended not to contain in curable mixtures, characterized in that alcohols of the formula / H 'and R 1' each represent a hydrogen atom, a halogen atom, a glycidoxy group or a hydroxyl group, at least one of the radicals R the formula -CH / H- —CH CH CH — R, ICH2I —CH N CH CH — R, CH CH, van in R 1, R 2, and R 3 wherein at least one of the radicals R 13, R 2 or R 3 represents a glycidoxy group. Process according to Claim 1, characterized in that the alcohol consists of tricyclo (5,2,1,026) 4 (or 3) -chlorodecane-3 (or 4), 8 (or 9) -diol. 3. A process according to claim 1, characterized in that the alcohol consists of tricyldo (5,2,1,02,) - decane-3 (or 4), 8 (or 9) -diol. 4. A process according to claim 1, characterized in that the alcohol is released from tricyclo (5,2,1,02,9-decane-3,4,8 (or 9) -trial. 4.