NO137289B - COUNTERWEIGHT VALVE. - Google Patents

Description

Process for the production of acetals.

The object of the present invention

nelse is a process for the production of acetals which are suitable as components for lamination resins, coating compounds,

lacquers, ' dipping resins, casting resins, putty compounds, pressing compounds or adhesives

clay and containing at least two epoxide

groups and which have the formula

in which Xt and X., mean hydrogen atoms el-

ler methyl groups, Z means epoxyalkyl radical or glycidyloxyalkyl radical, a radical with pre-

the flour

in which R,—R 9 mean hydrogen atoms, halogen atoms or lower alkyl residues, wherein R,

and R5 also together can mean a methylene-

group, the rest with formula

or a remainder with a formula

in which X3 and X4 mean hydrogen atoms or methyl groups, R',—R'8 hydrogen atoms, halogen atoms or lower alkyl residues, since R^ and R'5 together can also mean a methylene group, G means the residue obtained by splitting off both hydroxyl groups of a saturated aliphatic or cycloaliphatic diol or polyalkylene glycol or the residue of formula

IN

and p means an integer with a value of 1 or 2, n means an integer with a value from 1 to 3 and Y means when n = 1, a remainder with formula

in which R'^—R"8 mean hydrogen atoms, halogen atoms or lower alkyl residues, since R" and R"5 together can also mean a methylene group, when n is greater than 1 the residue obtained by separation of 4—6 hydroxide groups of a saturated aliphatic polyalcohol with 4-6 hydroxyl groups, characterized by treating acetals which contain at least one epoxidizable group and which have the formula in which X,, X2 and n have the meaning given above, Z' means the remainder with the formula where Hal = bromine or chlorine, a residue of the formula an alkenyl residue, a residue of formula in which the symbols R,—RH have the same meaning as above, the residue of formula or a residue of formula in which the symbols X3, X4, R',—R'a > G and p have the same meaning as above, and Y' means when n = 1 a remainder with formula

wherein R" i—R" 8 has the same meaning as above, when n is greater than 1, the same residue as Y, with epoxidizing agents.

The term "residue containing an epoxidizable group" is also understood to mean residues with epoxidizable C=C double bonds, such as an allyl residue, a butenyl residue or a tetrahydrobenzyl residue. In case of impact, e.g. of organic peracids such C = C double bonds can be epoxidized to 1,2-epoxy group.

The term "residue that contains an epoxidizable group" shall further also mean residues with a halohydrin grouping:

(Hal = halogen atom), such as a (3-methyl-glycerin-a-monochlorohydrin residue or a glycerine-a-monochlorohydrin residue. As is known, such a halohydrin group can also be transferred by treatment with dehydrohalogenating agents to a 1,2 -epoxy group.

The unsaturated acetals which are used as starting compounds in the process according to the invention are most easily available when, in a first step, methacrolein or preferably crotonaldehyde or acrolein is acetalized, either with the unsaturated dialcohol or with the saturated polyalcohol with 4-6 hydroxyl groups.

Hereby, two cases are separated.

1. The polyalcohol used already has at least one unsaturated group, which in another step is either directly epoxidized or, after addition of an alcohol with the formula Z - OH or Z' - OH, can be transferred to an epoxide compound. In this case, polyalcohols containing at least two hydroxyl groups can be used. 2. The polyalcohol is free of double bonds, in which case it must have at least four hydroxyl groups. The unsaturated dialcohols corresponding to the formula in which R'\—R"8 means halogen atoms, alkyl residues with 1—4 carbon atoms or hydrogen atoms, since R"] and R"5 together can also mean a methylene group. Examples of such dialcohols I should be mentioned: 1,1 - bis-[oxymethyl]-cyclohexene-(3), 1,1-bis-[oxymethyl]-6-methylcyclohexene-(3), 1,1-bis- [oxymethyl]-2,4,6-trimethyl-cyclohexene- (3), 1,1-bis-[oxymethyl]-2,5-endomethylene-cyclohexene(3)-and 1,1-bis-[oxymethyl]-4-chloro-cyclohexene- (3).

The following are mentioned as saturated polyalcohols with four to six hydroxyl groups: Erythrite, xylite, arabite, sorbitol, mannitol, dulcite, tallite, idite, adonite and pentaerythrite. The acetalization can take place according to methods known per se, such as e.g. by heating an aldehyde with the formula together with di- or polyalcohol in the presence of an acidic catalyst, such as e.g. hydrochloric acid or p-toluenesulfonic acid. Thus, you first get to the unsaturated ones acetals with the formula To get to the acetals used as starting material, in the first step an alcohol with the formula Z' - OH is added to the double bond in the unsaturated acetal III. As alcohols Z' - OH, glycerine-α-bromohydrin and particularly glycerine-α-monochlorohydrin, further mixtures of such monochlorohydrins, such as e.g. the technical mixture of glycerine-p-monochlorohydrin and glycerine-a-monochlorohydrin, further unsaturated alcohols, such as allyl alcohol, crotyl alcohol, oleyl alcohol, dihydrodicyclopentadienol-8 and especially those with the formula

in which R,—RH means halogen atoms, lower alkyl residues with 1—4 carbon atoms or hydrogen atoms, and since R, and R 5 together can also mean a methylene group. As such alcohols IV shall e.g. mention: AH-tetrahydrobenzyl alcohol, 6-methyl-A3-tetrahydrobenzyl alcohol, 2,4,6-trimethyl-A"-tetrahydrobenzyl alcohol, 1,5-endomethylene-A:1-tetrahydrobenzyl alcohol and 4-chloro-A:1-tetrahydrobenzyl alcohol.

If the unsaturated acetal III is derived from an unsaturated dialcohol, 2 mol of such an acetal can be added to 1 mol of a dialcohol.

Such polyhydroxyl compounds are above all aliphatic or cycloaliphatic dialcohols, such as ethylene glycol, diethylene glycol, triethyl glycol, polyethylene glycol, propanediol, polypropylene glycol, butanediol, pentanediol, hexanediol, quinine, resorcite.

Epoxidizable acetals are thus formed, e.g. of the type

(G = the residue of the dialcohol), i.e. the residue Z' in formula (III) is a residue with the formula

As examples, mention should be made of the addition products of 2 mol of the acetal of acrolein and 1,1-bis-(oxymethyl)-cyclohexene-3

to 1 mol of a glycol or polyglycol, such

such as ethylene glycol.

Instead of a dialcohol or glycol, water can also be used for the aggregation of 2 moles of an unsaturated acetal (VI), which is derived from an unsaturated dialcohol. One thus arrives at the simple ethers with the formula

i.e. the remainder Z' is here again a remainder with the formula

Furthermore, one can also add 1 of an unsaturated acetal (IV) which is derived from the unsaturated dialcohol to 1 mol of a dialcohol. The free hydroxyl group in the obtained addition product can then be reacted with a monohalohydrin.

One can thus e.g. first add 1 mol of the acetal of acrolein and 1,1-bis-[oxymethyl]-cyclohexene-3 to 1 .mol of a glycol or polyglycol. The sedimentation product can then be treated with e.g. 1 mole epi-kk» rhydrin.

The addition of the alcohol Z' - OH to the C = C double bond of the aldehyde residue conveniently takes place in a manner known per se in the presence of basic catalysts, such as sodium hydroxide or in particular of acidic catalysts or Lewis acids, such as e.g. sulfuric acid or boron trifluoride.

According to the method according to the invention, the unsaturated acetals, which contain at least one epoxidizable group, such as an epoxidizable C=C double bond or a halohydrin group, are treated with epoxidizing agents.

According to the invention, the epoxidation of the C=C double bond takes place according to common methods, preferably with the help of organic peracids, such as peracetic acid, perbenzoic acid, peradipic acid, monoperphthalic acid, etc. Chloric acid can also be used as an epoxidizing agent, as HOC1 is deposited in a first step to the double bond, and in a second step arise under the influence of an HCl-releasing agent, e.g. strong alkalis, the epoxide group.

In accordance with what has been said above about the meaning of the term "residue containing an epoxidizable group"

the treatment according to the invention with epoxidizing agents also includes the effect of halide-releasing agents, such as potassium hydroxide or sodium hydroxide on halohydrin groups, e.g. the glycerin monochlorohydrin group, forming the corresponding 1,2-epoxide group or a glycidyl group.

If the unsaturated acetals used as starting materials contain both epoxidizable C = C double bonds and halohydrin groups, the epoxidation takes place in two stages. Appropriately, the C = C double bond is first epoxidized and finally the halohydrin group is converted to epoxide groups.

During the epoxidation, in addition to di- or polyepoxides according to side reactions, fully or only partially hydrolyzed epoxides can also occur, i.e. compounds where the epoxide group in the polyepoxide of formula (I) has been fully or partially saponified into hydroxyl groups.

It was determined that the presence of such by-products usually has a beneficial effect on the technical properties of the cured polyepoxides. Therefore, it is generally recommended to omit isolation of the pure polyepoxides from the reaction mixture.

The diepoxide compounds with the general formula have particularly advantageous properties

in which X2 means a methyl group or a hydrogen atom and R,—R,, and R'^—R"() means halogen atoms or alkyl radicals with 1-4 carbon atoms or means hydrogen atoms, with R, and R5 respectively R", and R". - together can mean a methylene group. The most readily available are the diepoxide compounds having the formula

wherein X2 means a hydrogen atom or a methyl group and R and R" mean hydrogen atoms or lower alkyl radicals.

These epoxies are light, viscous or fusible resins, which with suitable hardeners, e.g. dicarbonic anhydrides, can be transferred to clear and bright cured products with excellent technical properties, such as particularly exceptionally high heat resistance according to Martens.

The diepoxide compounds with the formula also have similar interesting technical properties

respectively in which the radicals X2, R",—R"s respectively R" have the same meaning as in the formulas VII and VIII respectively. Furthermore, due to their advantageous properties, the polyepoxide compounds with the general formula in which X2 means a hydrogen atom or a methyl group are distinguished and the residues R,—R9 have the same meaning as in formula VII and A means a tetravalent aliphatic hydrocarbon residue containing at least 4 carbon atoms and which does not contain any carbon atoms with more than a single free valence. The most easily accessible here again are the diepoxide compounds with the formula

in which X2 means hydrogen atoms or methyl groups and R means hydrogen atoms or lower alkyl residues and A' means a tetravalent saturated aliphatic hydrocarbon residue, containing 4 to 6 carbon atoms and containing no carbon atoms with more than a single free valence, further to carbon atoms with a so free

valence no hydroxyl groups are attached.

These epoxies are light, fusible resins, which with suitable curing agents, e.g. dicarbonic anhydrides, can be transferred to clear and bright, hardened products with excellent technical properties.

Furthermore, mention must be made here of the triepoxide compounds with the formula in which X2 means hydrogen atoms or methyl groups and R means hydrogen atoms or lower alkyl residues and A" means a six-valent, saturated, aliphatic hydrocarbon residue, which contains 6 carbon atoms and which does not contain any carbon atoms with more than a single free valence.

These epoxides have similar properties to the epoxides of formula XII.

Furthermore, the diepoxide compounds have the general formulas

respectively, in which the residues Xs, X„ R', R", R', to R's and R", to R"s have the same meaning as previously indicated, in which G means an aliphatic or cycloaliphatic hydrocarbon residue, which is optionally interrupted by oxygen atoms, and in which p means an integer with a value of 1 or 2, particularly of practical importance. These preferred diepoxide compounds with the formulas VII, IX, XI or XIV are most easily obtained by treating hydroaromatic acetals with the formulas respectively, respectively, when the residues X2, X3, R to R9, R', to R's, R" to R"8, A, G and p have the same meaning as previously indicated, with epoxidizing agents. The acetals of formula XV and XVII are most easily reached in the following way. acetalizes acrolein or crotonaldehyde with a dialcohol of formula I and thus arrives at an acetal of the formula

A hydroaromatic alcohol with formula IX is then deposited, respectively dihydrodicyclopentadienol to the acetal XX.

The acetals of formula XVIII are most easily accessible as follows: One acetalizes acrolein or crotonaldehyde with a polyalcohol, which contains four to six hydroxyl groups, and obtains a spirocyclic acetal of the formula

2 mol of a hydroaromatic alcohol with the formula IV is then added to 1 mol of the acetal XXI.

Derivatives of dihydrodicyclopentadienol can be obtained in a similar way, id ot

2 mol of dihydrodicyclopentane dienol are added to 1 mol of acetal XXI.

Acetals of formula XIX are most easily obtained by adding 2 mol of an acetal of formula XX, either to 1 mol of H20 (p = 1) or to 1 mol of a dialcohol with the formula HO-G-OH (p = 2).

The oxidized acetals produced by the method according to the invention react with the usual hardeners for epoxy compounds. They can therefore be cured by adding such hardeners analogously to other polyfunctional epoxy compounds, respectively epoxy resins or network formation. Examples of such hardeners include basic or particularly acidic compounds.

The following have been found to be suitable: Amines or amides, such as aliphatic and aromatic primary, secondary and tertiary amines, e.g. mono-, di- and tri-butylamines, p-phenylenediamine, bis-[p-aminophenyl]-methane, ethylenediamine, N,N-diethylethylenediamine, N,N-dimethylpropylenediamine, diethylenetriamine, tetra-[oxyethyl ]-diethylenetriamine, triethylenetetramine, tetraethylenepentamine, trimethylamine, diethylamine, triethanolamine, Mannich bases, piperidine, piperazine, guanidine and guanidine derivatives, such as phenyldiguanidine, diphenylguanidine, dicyandiamide, aniline formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, polymers of ami- nostyrols, polyamides, e.g. such as aliphatic polyamines and di- or trimerized unsaturated fatty acids, isocyanates, isothiocyanates, polyhydric phenols, e.g. resorcinol, hydroquinone, bis-[4-oxyphenyl]-dimethylmethane, quinone, phenolaldehyde resins, oil-modified phenolaldehyde resins, reaction products of aluminum alcoholates or -phenolates with tautomerically reacting compounds of the aceted diester type, Friedel Crafts catalysts, e.g. e.g. A1C13, SbCl5, SnCl4, ZnCl2, BF3 and their complexes with organic compounds. see, phosphoric acid. Polybasic carboxylic acids and their anhydrides are preferably used as hardeners, e.g. phthalic anhydride, methylene indomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride or endomethylenetetrahydrophthalic anhydride or their mixtures. Maleic or succinic anhydride, optionally using accelerators, such as tertiary amines, or strong Lewis bases, such as e.g. alkali alcohols, further preferably polyhydroxyl compounds, such as hexanetriol, glycerin.

It was found that when curing the epoxide resins according to the invention with carbonic anhydrides, preferably on 1 gram equivalent of epoxide groups, only approx. 0.3 to 0.9 gram equivalents of anhydride groups. When using basic accelerators, such as alkali alcoholates or alkali salts of carboxylic acids, up to 1.0 gram equivalents of anhydride groups can be used.

The term "hardeners", as used herein, means the conversion of the above epoxy compounds into insoluble and infusible resins.

The curable mixtures also preferably contain a portion of otherwise corresponding acetals, whose epoxide groups are, however, wholly or partially saponified into hydroxyl groups and/or other network-forming polyhydroxyl compounds, such as hexanetriol. Of course, the curable epoxy compounds can also be added to other epoxides, such as e.g. mono- or polyglycidyl ethers of mono- or polyalcohols, such as butyl alcohol, 1,4-butanediol or glycerin, respectively of mono- or polyphenols, such as resorcin, bis-[4-oxyphenyl]-dimethylmethane or condensation products of aldehydes with phenols

(novolacquers), further polyglycidyl esters of

polycarboxylic acids, such as phthalic acid, as well as further aminopolyepoxides, such as those e.g. is obtained by dehydrohalogenation of the reaction products of epihalohydrins and primary or secondary amines, such as n-butylamine, aniline or 4,4'-di-[monomethylamino)-diphenylmethane.

The hardenable epoxy compounds or their mixtures with hardeners can continue before the hardening on one or the other

In the first step, fillers, plasticizers, coloring substances etc. are added. As a stretching and filling agent, e.g. asphalt, bitumen, glass fibres, mica, quartz flour, cellulose, kaolin, finely divided silicic acid (Aero-sil) or metal powder are used.

The mixtures of the epoxy compounds produced by the method according to the present invention and the hardeners can, in the unfilled or filled state, optionally in the form of solutions or emulsions, serve as textile aids, laminating resins, painting agents, varnishes, dipping resins, casting resins, ironing, filling and putty compounds, adhesives, pressing compounds and the like as well as for the production of such agents. The new resins are particularly valuable as insulating compounds for the electrical industry.

In the following examples, parts mean parts by weight, percentages by weight, the ratio between parts by weight and parts by volume is the same as for kg and litres, the temperatures are indicated in degrees Celsius.

Example 1.

a) Acetal of acrolein and 1, 1- bis-[oxymethyl'] - cyclohexene- 3.

118 parts of acrolein, 286 parts of 1,1-bis-[oxymethyl]-cyclohexene-3 and 3 parts by volume of 50% sulfuric acid are heated together for 20 minutes to 50° C. After everything has dissolved, 700 parts by volume of benzene are added and 2 parts of p-toluenesulfonic acid and boil for 40 minutes in a circulating distillation apparatus until 40 parts of water have been azeotropically distilled off. 4 parts of anhydrous sodium carbonate are added to the solution, filtered and evaporated. After expelling the benzene,

distilled in vacuum at 54-61° C (0.2 mm Hg) 319 parts of acetal (3-vinyl-2,4-di-oxospiro(5,5)-undecene-9) above, which corresponds to a yield of 87 percent of the theoretical. This leaves 40 parts of an unidentified residue. b) Addition of As-tetrahydrobenzyl alcohol. A mixture of 225 parts of the acetal described above (3-vinyl-2,4-dioxo-spiro(5,5)-undecene-9), 140 parts of Aa-tetrahydrobenzyl alcohol, 0.5 parts by volume of concentrated H 2 SO 4 and 0.5 parts by volume of one; A 50% solution of BF3 in diethyl ether (BF3 exists as etherate) is heated to 80° C and then cooled. You get 360 parts ay of a brown liquid, in which no tetrahydrobenzyl alcohol can any longer be detected. It consists mainly of 3-[A3-tetrahydrobenzyloxyethyl]-2,4-dioxospiro(5,5)-undecene-9. c) Epoxy coating. 320 parts of the above-described 3- [A'-tetrahydrobenzyloxyethyl]-2,4-dioc- sospiro(5,5)-undecene-9 (crude product) is dissolved in 1000 parts by volume of benzene and 25 parts of sodium acetate are added. For 20 minutes, while stirring, 462 parts of 39.5% peracetic acid are added in portions. During intense cooling, the temperature is kept at approx. 35° C. After the mixture has reacted further for 2 hours at 30° C with constant stirring, the reaction is finished and it is cooled to room temperature. Titration shows consumption of the theoretical amount of peracetic acid. The benzoic solution is washed neutrally with three times 30 parts by volume of water and then with aqueous caustic soda. It is then washed again with twice 150 parts by volume of water. The benzoic solution is dried over sodium sulphate, filtered and evaporated in vacuo. The last remaining solvent is removed in high vacuum at 100° C. 317 parts of a light yellow liquid resin are obtained with an epoxide content of 5.3 epoxide equivalents/kg and a viscosity at 20° C of cvd25,000 cP. This mainly consists of the diepoxide with the formula

Example 2.

a) Acetal of acrolein and 1,1-bis-[oxymethyl]-6-methyl-cyclohexene-3. 56 parts acrolein, 157 parts 1,1-bis-[oxymethyl]-6-methyl-cyclohexene-3 and 1 part 50% sulfuric acid is heated together in a water bath to 40° C until everything is dissolved. An exothermic reaction occurs, so that after removal from the water bath the temperature rises to 50° C. Now add 350 parts by volume of benzene and boil for 40 minutes in a circulating distillation apparatus until 20 parts of water have been azeotropically distilled off. 2 parts of anhydrous sodium acetate are added to the solution, filtered and evaporated. After stripping off the benzene, 163 parts of acetal-[3-vinyl-7-methyl-2,4-dioxospiro-(5,5)-undecene-9] distil in vacuo at 81° C. (0.5 mm Hg), which corresponds to a yield of 83.6 per cent of the theoretical. This leaves 27 parts of an unidentified remainder. b) Addition of A°-tetrahydrobenzyl alcohol.

One mixture of 65 parts of the above-

for the described acetal [3-vinyl-7-methyl-2,4-dioxospiro(5,5)-undecene-9], 38 parts of A'-tetrahydrobenzyl alcohol, 0.5 parts of concentrated H.SO., and 0.5 parts of a 40% solution of BF3 in diethyl ether (BF, available as etherate) is heated to 80° C. for 4 hours. You let it stand for 15 hours, shake with 2 parts anhydrous Na..C03 and get 101 parts

of a liquid in which no tetrahydrobenzyl alcohol can any longer be detected. This mainly consists of 3-[A<:>"-tetrahydro-benzyl-oxyethyl]-7-methyl-2,4-dioxo-spiro(5,5)-undecene-9.

c) Epoxy coating.

97 parts of the above-described 3- [ A"-tetrahydrobenzyloxyethyl]-7-methyl-2,4-dioxospiro(5,5)-undecene-9 is dissolved in 28 parts by volume of benzene. After adding 7 parts of anhydrous sodium acetate, 148 parts of 39.5 ps.-ig are added dropwise while stirring per- external cooling the temperature is kept at 30— acetic acid within 30 minutes. Using 35° C. After 2 hours, 91 per cent has been consumed. of the theoretical amount of peracetic acid. After 3 hours it is allowed to cool to room temperature, the lower aqueous phase is separated and the upper phase is washed with 3 times 100 parts by volume of water, then neutralized by shaking with 100 parts by volume of H.O + 7 parts by volume of 30% NaOH. Then wash once more with twice 50 volumes parts of water, dried over sodium sulfate, filtered and evaporated in vacuo at 0.15 mm Hg at 100° C. 774 parts of a liquid, pale yellow resin with a content of 4.5 epoxide equivalents/kg and a viscosity at 20° C are obtained of 27.474 cp. This resin mainly consists of the diepoxide with the formula

Example 3.

a) Acetal of crotonaldehyde and 1, 1-bis- [oxymethyl]-cyclohexene-3. 70 parts of crotonaldehyde, 143 parts of 1,1-bis-[oxymethyl]-cyclohexene-3 and 0.8 parts by volume of 50% H.SC-4 are heated together for 15 minutes more 50° C until everything is dissolved and an exothermic reaction occurs. Now 350 parts by volume of benzene are added and it is boiled for 30 minutes in a circulating distillation apparatus until 18 parts of water have been azeotropically distilled off. 2 parts of anhydrous sodium acetate are added to the solution, filtered and evaporated. After stripping off the benzene, distilling in vacuo at 92° C (0.5 mm Hg), 180 parts of acetal [3-propenyl-2,4-dioxospiro(5,5)-undecene-9], which corresponds to a yield of 92 percent .of the theoretical. b) Addition of A' tetrahydrobenzyl alcohol. A mixture of 176 parts of the above-described acetal [3-propenyl-2,4-dioxospiro(5,5)-undecene-9], 105 parts of A<3->tetrahydrobenzyl alcohol and 0.8 parts by volume of 50 percent ig HSO, is heated for 8 hours to 80° C. It is allowed to stand for 15 hours and freed from unreacted tetrahydrobenzyl alcohol by evaporation in a vacuum, whereby 19 parts of the alcohol distill off at 40° C (0.15

mm Hg). 253 parts of residue remain, corresponding to a crude yield of 92 per cent, which mainly consists of 3-[A"'-tetrahydrobenzyloxy-(2')-propyl]-2,4-dioxo-spiro(5, 5)-undecene-9.

c) Epoxy coating.

253 parts of the above-described 3-[A"'-tetrahydrobenzyl-oxy-(2')-propyl]-2,4-dioxospiro (5,5)-undecene-9 are dissolved in 750 parts by volume of benzene. After addition of 20 parts of anhydrous sodium acetate are added dropwise while stirring to 340 parts of 39.5% peracetic acid within 45 minutes. With the help of external cooling, the temperature is kept at 30-35° C. After 2 hours, the theoretical amount of peracetic acid has been consumed. Allow to cool to room temperature , the lower aqueous phase is separated and the upper phase is washed three times with 150 parts by volume of water, then neutralized by shaking with 100 parts by volume of water + 7 parts by volume of 30% NaOH.

times with twice 10 parts by volume of water, dried over sodium sulfate, filtered and evaporated in vacuo at 100° C. (15 mm Hg) for 30 minutes. 774 parts of a viscous yellow resin are obtained with a content of 5.1 epoxide equivalents/kg and a viscosity at 20° of 102,700 cp.

This resin mainly consists of the diepoxide with the formula

Example 4.

In an analogous manner as described in the preceding examples, the acetal is prepared from 107 parts of crotonaldehyde and 229 parts of 1,1-bis-[oxymethyl]-6-methyl-cyclohexene-3 in the presence of 1 part of 50% sulfuric acid and of benzene for the azeotropic distillation of the still water. During the fractionation in vacuum, at 75-82° C. (0.2 mm Hg) 270 parts of 3-propenyl-7-methyl-2,4-dioxospiro(5,5)-undecene-9 are converted.

A mixture of 158 parts of this acetal, 75 parts of 6-methyl-A'-tetrahydrobenzyl alcohol and 1.5 parts of a 40% solution of BF" in diethyl ether is heated for 2 hours to 80° C. After distillation of 30 parts of the reaction at 140° C (0.1 mm Hg), 230 parts of residue remain, which mainly consists of the addition product 3-[6"-methyl-A"'-tetrahydrobenzyloxy-(2')-propyl-7 -methyl-2,4-dioxospiro (5,5)-undecene-9.

215 parts of this addition product are mixed with 600 parts by volume of benzene and 16 parts of sodium acetate are added. The stirred mixture is added in portions at 30° C. 249 parts of 42% peracetic acid. After 2 hours, the theoretical amount of peracetic acid has been consumed. It is then processed as described in the previous examples. After evaporation at 100° C (0.1 mm Hg) a light, viscous resin is obtained with an epoxide content of 4.7 epoxide equivalents per kg. This mainly consists of the diepoxide with the formula

and can be cured with phthalic anhydride to a light, infusible resin.

Example 5.

A mixture of 22 parts of the cyclic acetal of 2 moles of acrolein and 1 mole of pentaerythritol (designated as 3,9-divinyl-spirobi-[m-dioxane] or 3,9-divinyl-2,4,8,10-te- traoxospiro(5,5)-undecane) and 22 parts of A<3->tetrahydrobenzyl alcohol are added to 0.1 part of 60% sulfuric acid and 0.2 parts of a 40% solution of BF,, in diethyl ether. The mixture is heated for 12 hours to 80° C. After this time, a viscous yellow-brown product has formed, in which no tetrahydrobenzyl alcohol can be detected and which mainly consists of the addition product 3,9-bis-[A''-tetrahydrobenzyl- oxyethyl]-spirobi-[m-dioxane].

45 parts of the above-described addition product are dissolved in 140 parts by volume of benzene and 4 parts of sodium acetate are added. For 15 minutes, 40 parts of 42.8% peracetic acid are added dropwise with constant stirring. By means of ice cooling, the temperature is kept at 30° C. After the mixture has been stirred further for 60 minutes at 30° C, the lower aqueous phase is separated. The benzoic solution is washed with twice 50 parts by volume of water, dried over sodium sulphate and evaporated. A viscous resin with an epoxide content of 2.70 epoxide equivalents/kg is obtained. This resin mainly consists of the diepoxide with the formula

and can be cured with phthalic anhydride to a light infusible resin.

Example 6.

A mixture of 91 parts of the cyclic triacetal of 3 mol of acrolein and 1 mol of sorbitol, 105 parts of A'-tetrahydrobenzyl alcohol and 0.5 part of a 45% solution of BF„ in diethyl ether is heated for 5 hours to 80°C It is allowed to cool and then distilled at 45° C. and a vacuum of 0.15 mm Hg 30 parts of unreacted tetrahydrobenzyl alcohol. The remainder thus consists of an addition product of exactly 2 mol of the alcohol to 1 mol of the triacetal. This addition product is epoxidized as follows: 153 parts of the residue described above are dissolved in 350 parts by volume of benzene and 7 parts of sodium acetate are added. For 35 minutes, 134 parts of 35.8% peracetic acid are added dropwise with constant stirring. During ice cooling, the temperature is kept at 30-35° C. After the mixture has been stirred for a further 60 minutes at 30° C, the theoretical amount of peracetic acid has been consumed. Allow to cool and separate the lower aqueous phase. The benzolic solution is washed twice with 100 parts by volume of water and once with 100 parts by volume of aqueous 2-N. NaOH solution. It is further washed with twice 50 parts by volume of water, then dried over sodium sulphate, filtered and evaporated in vacuo, finally at 100° C (0.5 mm Hg). 159 parts of a yellow viscous resin with an epoxide content of 2.1 epoxide equivalents/kg are obtained. This resin can be cured with phthalic anhydride to a light infusible resin.

Example 7.

A mixture of 23 parts of glycerine-α-monochlorohydrin and 36 parts of the acetal of acrolein and 1,1-bis-[oxymethyl]-cyclohexene-3 prepared according to example 1 is added to 0.5 parts of a 40% solution of BF, in diethyl ether and heated for 80 minutes to 80° C. In the obtained addition product (3-[2'-oxy-3'-chloro-propoxyethyl]-2,4-dioxospiro(5,5)-undecene-9) the cyclo-olefinic double bond is epoxidized as follows: 150 parts of benzene and 5 parts of anhydrous sodium acetate are added to the above unreacted reaction mixture (approx. 59 parts). While stirring and ice-cooling, 36 parts of 42.8% peracetic acid are added dropwise for 30 minutes at 30° C. The mixture is then stirred for a further 60 minutes at 30° C. The theoretical amount of acetic acid is then consumed and it is worked up as described in the previous examples. You thus get 52 parts of mono-epoxidized chlorohydrin.

The monoepoxide obtained is transferred

which follows to a diepoxide:

52 parts of the above-described epoxidized chlorohydrin (3-[2'-oxy-3'-chloro-propoxyethyl]-9,10-epoxy-2,4-dioxo-spiro(5,5)-undecene) are added to 27 parts 28 pst.-ig aqueous caustic soda and heated for 1 hour to 50° C. Now 100 parts of benzene are added and the separated solid NaCl is filtered off. The benzoic layer is separated, washed neutrally and finally evaporated under high vacuum. You get 42 parts of a light yellow, liquid epoxy resin, which mainly consists of the di-epoxide compound with the formula

It can be cured with phthalic anhydride to an almost colorless, infusible resin.

Example 8.

A mixture of 45 parts of glycerine-a-monochlorohydrin and 4 parts of the cyclic acetal of 1 mol of pentaerythritol and 2 mol of acrolein (3,9-divinylspirobi[m-dioxane]) is added to 0.5 parts of a 45 percent-ig resolution of BF,. Within 15 minutes, a weak exothermic reaction is observed. After completion of this, no more free glycerin-a-monochlorohydrin can be detected in the reaction mixture. It is allowed to cool, 63 parts of 28% aqueous caustic soda are added and heated with vigorous stirring for one hour to 45° C. The precipitated solid NaCl is filtered off, separated from the benzoic layer and the solvent is evaporated. As a residue, 70 parts of a viscous light yellow resin with an epoxide content of 1.8 epoxide equivalents/kg are obtained. This mainly consists of the diepoxide with the formula

and can be cured with phthalic anhydride to a faintly colored infusible resin.

Example 9.

In 100 parts of the polyepoxy resin produced according to example 1, phthalic anhydride is dissolved as a curing agent at 120-125°C, with 0.45 equivalents of anhydride groups being used in a first sample and 0.65 equivalents of anhydride groups per equivalent epoxide groups. At 120° C, the mixtures have a viscosity of less than 10 cP.

A first part of the mixtures is poured into aluminum molds (40 x 10 x 140 mm) and hardened for 24 hours at 140° C. The resulting casting has the following properties:

Another part of the above mixtures is poured in layer thicknesses of approx. 1/10 and 1 mm on glass plates and then cured uniformly for 24 hours at 140° C. The thus cured film shows excellent adhesion to the substrate and is resistant to 5N after one hour's exposure at room temperature. -sulphuric acid, 5N . - caustic soda, water, acetone or chlorobenzene.

Example 10.

100 parts of the polyepoxy resin prepared according to example 1 are mixed at room temperature with 11.9 parts of 2,4-dioxy-3-oxymethylpentane. In this mixture, 51 parts of phthalic anhydride are dissolved as hardening agent at 120 to 125° C. The mixture which is completely in aluminum forms, as described in example 9, (approx. 90 g), is gelatinized at 120° C for approx. 1 hour, i.e. the initially liquid mixture has solidified into a gel. After 24 hours of curing at 140° C, the casting shows an impact bending strength of 12.7 cmkg/cm<2> and a bending strength of 16.0 kg/mm<=>.

Example 11.

51 parts of phthalic anhydride (0.65 equivalents of anhydride groups per equivalent of epoxide groups) are dissolved at 120-130° C in 100 parts of a polyepoxy resin prepared according to example 1. At 120° C, the mixture has a viscosity of less than 10 cP and after 2y2 hours a viscosity of 1500 cP.

The mixture is poured, as described in example 9, into aluminum molds. The curing is carried out in 2 stages, first curing for 24 hours at 140° C and then 24 hours at 200° C. The resulting casting has an extremely high heat resistance (measured according to Martens DIN) of > 235° C.

Example 12.

5.94 parts of a Na alcoholate, which was prepared by dissolving 0.41 parts of sodium metal at approx. 120° C. in 100 parts of 2,4-dioxy-3-oxymethyl-pentane is dissolved at room temperature in 100 parts of the epoxy resin prepared according to example 1. As a curing agent, 1.0 equivalents of phthalic anhydride per equivalent epoxy groups at 120-125° C. A first part of the mixture is poured, as described in example 9, into aluminum molds and hardened for 24 hours at 140° C. The casting thus obtained shows the following properties:

Another part of the above mixture is used for the production of adhesives. For this purpose, degreased and sanded aluminum sheets (170 x 25 x 1.5 mm, overlap 10 mm), which are available under the name "Anti-corodal B", were glued together. The curing for the adhesive joints is carried out for 24 hours at 140° C.

The following tensile shear strengths are obtained at different test temperatures:

Above all, the bonds show excellent tensile shear strengths at the extremely high test temperatures of 150-190° C.

Example 13.

100 parts of the polyepoxy resin prepared according to example 3 are fused together with 45.6 parts of phthalic anhydride as a curing agent at 120-125° C, with 0.6 equivalent anhydride groups being used for 1 equivalent of epoxy groups of the resin. The mixtures are hardened in an aluminum mold (40 x 10 x 140 mm) for 24 hours at 150° C. The thus hardened casting body shows an impact bending strength of 13.9 cmkg/cm- and a bending strength of 10.1

kg/mm<2>.

Example 14.

In 50 parts of the polyepoxide resin prepared according to example 3, 2.5 parts of a BF, monoethylamine complex are dissolved. The mixture is poured into an iron mold and hardened for 16 hours at 150° C. The resulting casting shows a heat resistance (measured according to Martens DIN) of 138° C.

Example 15.

The mixture of 86 parts of ethylene glycol and 550 parts of the acetal obtained according to example 1 (a) of 1,1-bis-[oxymethyl]-cyclohexene-3 and acrolein (3-vinyl-2,4-dioxospiro-5,5 -undecen-9) to

80° C, add, while stirring, 1 part of concentrated sulfuric acid, whereby a slight rise in temperature takes place. The reaction mixture is now kept for 2 hours at 85-90° C, first under slight cooling and after the end of the heating effect by heating with the aid of an oil bath. The acid is then neutralized by adding 2 parts sodium carbonate and 41 parts excess acetal is distilled off from the reaction mixture, which passes at 55° C. and 0.3 mm Hg. The ethylene glycol has reacted completely. 578 parts of crude ethylene glycol bis-[2-(2',4'-dioxo-spiro-5',5'-undecen-9'-yl-3')-ethyl]-ether are obtained as a distillation residue in the form of a light brown oil.

The 578 parts of the addition product described above are taken up in 1700 parts by volume of benzene, 30 parts of sodium acetate (anhydrous) are added and the mixture is heated to 35° C. Now, within 30 minutes, 555 parts of 41.3% peracetic acid are allowed to drip in while maintaining of a temperature of 35° C, which is also maintained for a further two hours after instillation of the oxidizing agent. First, within approx. 1 1/2 hours is cooled slightly and then the temperature is maintained by adding heat. After the specified time, the theoretical amount of oxidizing agent has been consumed. It is now cooled and separated from the aqueous phase. The benzene layer is washed three times with 40 parts by volume of water, the third part of water to neutralize the acetic acid still present being added to a further 120 parts of 30% caustic soda. It is then washed once more with 200 parts by volume of water, the solvent is evaporated in a partial water jet vacuum and finally the residue is freed of the last traces of volatile components by heating to 100° C below 0.1 mm Hg. 563 parts of a light yellow oil are thus produced, which has an epoxide content of 4.18 epoxide equivalents/kg (95 per cent of the theoretical) and which mainly consists of the compound with the formula

When this oil is cured with phthalic anhydride (0.7 equivalents of anhydride groups per equivalent of epoxide groups) for 24 hours at 240° C, a faintly colored, easily pliable, firm, infusible resin is obtained.

Example 16.

198 parts of the acetal of acrolein and 1,1-bis-[oxymethyl]-cyclohexene-3 described in example 1 (a) are heated with 38 parts of trimethylene glycol to 80° C., 0.5 parts of concentrated sulfuric acid are added, observing a slight rise in temperature. The reaction mixture is then kept, as described in example 15, for two hours at 85-90° G, then 1 part sodium carbonate is added and then 18 parts excess of acetal is distilled off at 0.2 mm Hg. 210 parts of trimethylene glycol bis-[2-(2',4'-dioxo-spiro-5',5'-undecen-9'-yl-3')-ethyl]-ether remain in the form of a viscous yellow -like oil. This is epoxidized by taking it up in 600 parts by volume of benzene, adding 1 part anhydrous sodium acetate and allowing 198 parts of 40.7% peracetic acid to drip in within 30 minutes at 35° C. After further stirring for 2 hours at 35° C is 97 percent of the theoretical amount of oxidizing agent consumed. The further processing then takes place as described in example 15 and you finally get 198 parts of a light yellow oil, which has an epoxide content of 3.82 epoxide equivalents/kg (90 per cent of the theoretical) and which mainly consists of the diepoxide with the formula

The curing of this product with ftal-] acid anhydride, analogously to example 15,' leads to an easily pliable, firm, infusible1 resin.

Example 17.

A mixture of 46 parts of 1,4-butanediol and 200 parts of the acetal of acrolein and 1,1-bis-[oxymethyl]-cyclohexene-3 described in ex-I sample 1 (a) is heated to 80° C, adding 0.5 parts concentrated sulfuric acid, observing a slight rise in temperature. The temperature is maintained with good stirring for 2 hours at 85-90°C, first during slight cooling and after cooling the heat effect during heating. Then 1 part of anhydrous sodium carbonate is added and then 20 parts of excess acetal are distilled off at 50° C. and 0.3 mm Hg, which corresponds exactly to the excess added to begin with. 223 parts remain as distillation residue

butanediol bis-[2-(2',4'-dioxo-spiro-5',5',-undecen-9'-yl-3')-ethyl]-ether in the form of a dark-colored viscous oil.

The latter is epoxidized as follows:

The crude product is taken up in 600 parts by volume of benzene, 10 parts of anhydrous sodium acetate are added and then 196 parts of 40.8% peracetic acid are allowed to drip in at 35° C. for 30 minutes. The oxidation is carried on for 3 hours and is initially maintained by slight cooling, later by heating to the desired temperature of 35° C. After the specified time, 98.5 per cent of the theoretical amount of oxidizing agent has been consumed. The further processing takes place analogously to what is described in example 15. After removing the last traces of volatile components in a high vacuum, one thus obtains 233 parts of a viscous, yellow liquid, which has an epoxide content of 3.95 epoxide equivalents per kg (94.5 per cent of the theoretical) and which mainly consists of the diepoxide with the formula

After curing this product for 24 hours with phthalic anhydride (0.7 equivalents of anhydride groups per equivalent of epoxide groups) at 140° C, a light yellow, easily flexible, firm, infusible resin is obtained.

Example 18

The mixture of 78 parts of pentanediol-1,5 and 298 parts of the acetal of acrolein and 1,1-bis-[oxymethyl]-cyclohexene-3 described in example 1 (a) is heated to 80° C, 1 part of concentrated sulfuric acid is added and notes a slight rise in temperature. For 3 hours the temperature is kept at 85-90° C and then neutralized with 1 part anhydrous sodium carbonate. Then, 20 parts of excess acetal are removed by vacuum distillation, and 349 parts of pentanediol-bis-[2-(2',4'-dioxo-spiro-5',5'-undecen-9'-yl are obtained as a residue) -3')-ethyl]-ether in the form of a dark-colored, viscous liquid.

These 349 parts are taken up with 1050 parts by volume of benzene, 16 parts of anhydrous sodium acetate are added and epoxidized, as described in example 15, with 309 parts of 40.7% peracetic acid. The processing takes place analogously to what is described in example 15. You finally get 362 parts of a viscous, yellow liquid, which has an epoxide content of 3.84 epoxide equivalents/kg (95.3 per cent of the theoretical).

Example 19.

A mixture of 198 parts of the acetal of acrolein and 1,1-bis-[oxymethyl]-cyclohexene-3 described in example 1 (a) and 100 parts of polyethylene glycol with an average molecular weight of 200 is heated to 80° C. After adding 1 part sulfuric acid, the temperature is kept for 2 hours at 85-90° C. After neutralization with 1 part of anhydrous sodium carbonate, the excess of acetal is then distilled off at 0.2 mm Hg 17, and as a residue 270 parts of a brown, viscous liquid are obtained.

This is epoxidized after it is taken up in 800 parts by volume of benzene with 198 parts of 40.8 percent peracetic acid and after the addition of 10 parts of anhydrous sodium acetate. After washing and concentration, 273 parts of a viscous, yellow liquid are obtained, which has an epoxide content of 3.24 epoxide equivalents/kg (95.9 per cent of the theoretical).

Example 20.

298 parts of the acetal of acrolein and 1,1-bis-[oxymethyl]-cyclohexene-3 and 225

parts of a polyethylene glycol with an average molecular weight of 300 are heated together to 80° C. After the addition of 1 part of sulfuric acid and 0.5 parts of boron trifluoride etherate (48 per cent), no rise in temperature is observed. The temperature is then maintained for 3 1/2 hours by heating to 85-90° C,

is then neutralized and 23 parts excess of acetal is distilled off. This leaves 492 parts of a brown, viscous liquid.

This is taken up in 1470 parts by volume of benzene and, after the addition of 16 parts of anhydrous sodium acetate, is epoxidized with 310 parts of 40.8% peracetic acid for 3 hours at 35° C, whereby 100% of the theoretical part of the oxidizing agent has been consumed. After washing, neutralization and evaporation, 418 parts of a light yellow, viscous liquid with an epoxide content of 2.84 epoxide equivalents/kg are obtained. By curing for 24 hours at 140° C with phthalic anhydride (0.65 equivalents of anhydride groups per equivalent of epoxide groups) a flexible, infusible resin is obtained.

Example 21.

A mixture of 279 parts of the acetal of acrolein and 1,1-bis-[oxymethyl]-cyclohexene-3 and 319 parts of polypropylene glycol with an average molecular weight of 425 is heated to 85° C. 1 part of concentrated sulfuric acid is then added, whereby does not observe any heating effect. A further 0.5 parts of 40% boron fluoride etherate is then added. The temperature then rises very slightly and is held for 6 hours at 85-90° C. After neutralization with 3 parts sodium carbonate and distillation of excess acetal, 586 parts of a dark-coloured, viscous liquid remain.

The latter is epoxidized after it is taken up in 1,500 parts by volume of benzene and the addition of 14 parts of anhydrous sodium carbonate with 284 parts of 44.2 percent peracetic acid. The consumption of oxidizing agent is theoretical. After work-up, analogous to that indicated in example 15, 585 parts of a very viscous, yellow liquid with an epoxide content of 2.17 epoxide equivalents/kg (89 per cent of the theoretical) are obtained. The curing of this product with phthalic anhydride (1 equivalent of anhydride groups per equivalent of epoxide groups) gives very flexible and plastic objects.

Example 22.

369 parts of acetal of acrolein and 1,1-bis-[oxymethyl]-cyclohexene-3 and 106 parts of transkinite are heated to 80° C., whereby the kinite is only partially dissolved. After adding 1 part sulfuric acid, a slight rise in temperature is observed and the rest of the kinite slowly dissolves. The temperature is maintained for 3 hours at 90-95° C and then cooled, whereby the reaction mixture crystallizes.

458 parts of the mixture thus obtained are dissolved in 1200 parts by volume of benzene and 20 parts of anhydrous sodium carbonate are added. It is then heated to 35° C and within 30 minutes, 390 parts of 34.4% peracetic acid are allowed to drip in. It is then stirred for a further 2 hours at the same temperature. After cooling, the aqueous layer is separated and the benzoic layer is processed, as described in example 15. Thus, 427 parts of a faintly colored compound are obtained, which crystallizes on cooling and which has an epoxide content of 3.72 epoxide equivalents/kg (94.2 per cent of the theoretical).

By curing this product for 24 hours at 140°C with phthalic anhydride (1 equivalent anhydride group per equivalent epoxy group), cast objects with good mechanical properties are obtained.

Example 23.

A mixture of 217 parts of the acetal prepared according to example 3 (a), and 1,1-bis-[oxymethyl]-cyclohexene-3 and crotonaldehyde and 31 parts of ethylene glycol is heated to 80° C. 2 parts of sulfuric acid are then added, as no heat effect is observed. It is then heated using an oil bath to 105° C and a weak exothermic reaction is now observed. The temperature is kept at 105° C for a further 2 hours, then 2 parts of sodium carbonate are added and the excess of acetal is distilled over 15 parts. This leaves 227 parts of a viscous, dark-coloured liquid.

The latter is taken up in 660 parts by volume of benzene and epoxidized after the addition of

18 parts anhydrous sodium carbonate, thus

as described in example 15, with 216 parts 39.5 percent peracetic acid. After the work-up, which is analogous to that described in example 15, 211 parts of a very viscous, orange-coloured liquid with an epoxide content of 3.75 epoxide equivalents/kg (90.5 per cent of the theoretical) are obtained.

Example 24.

A mixture of 276 parts of the acetal of acrolein and 1,1-bis-[oxymethyl]-cyclohexene-3 and 225 parts of dihydro-dicycloheptandienol-8 is heated to 85° C and 0.5 parts of H2SO4 (98 per cent) are added. -ig). An instantaneous rise in temperature takes place. The temperature is maintained for 24 hours at 90° C, first by means of cooling and then by means of heating. The addition product obtained is then epoxidized as follows: 1,350 parts of benzene and 35 parts of sodium acetate are added and heated to 35° C. Then, 576 parts of peracetic acid (43.6 percent ig) are added over the course of 30 minutes. The temperature is still maintained for 2 and 2 hours at 35° C., first by cooling and then by heating. The product is then washed, neutralized and concentrated, as described in example 1 (c). You finally get 505 parts of a viscous, yellow liquid with an epoxide content of 5.15 epoxide equivalents/kg (93.3 percent of the theoretical), which mainly consists of the compound with the formula

This product is cured with phthalic anhydride (0.7 equivalent anhydride groups per equivalent epoxy group) for 24 hours at 140° C. A light, yellow, infusible resin with a Martens value (DIN) of 180° and with good mechanical properties is obtained.

Curing tests have been carried out with a commercial product "EP 201", as samples of this product with an epoxide content of 6.35 epoxide equivalents/kg were fused with phthalic anhydride as a curing agent at 120-130° C, with 1 equivalent epoxide group being used 0.65 and 0.90 equivalents of anhydride groups respectively. The mixtures were then poured into molds and cured for 24 hours at 140° C. The test on the mechanical dimensional stability in the heat according to Martens (DIN) for the cast objects obtained gave the following results: Martens value (DIN)

°C

Sample 1 (0.65 equivalents of phthalic anhydride per 1 epoxy equivalent) 163 Sample 2 (0.9 equivalents of phthalic anhydride per 1 epoxy equivalent 149

In contrast, the diepoxide according to example 24 and which is produced according to the method according to the present invention, which was fused with phthalic anhydride in a ratio of 0.7 equivalents of anhydride groups per 1 equivalent of epoxy groups, and then cures exactly as above for 24 hours at 140° C, a much higher Martens value (DIN) of 180° C.

Example 25.

A mixture of 268 parts of oleic alcohol and 186 parts of the acetal of acrolein and 1,1-bis-[oxymethyl]-cyclohexene-3 described in example 1 (a) is heated to 85° C and then 0.5 parts of H„ are added SO, (98 per cent). A slight heat development is observed. The temperature is maintained for 3 hours at 90° C. Then 1 part Na2-CO, is added and the mixture is heated to 110° C under 0.2 mm Hg, whereby nothing distills over. The resulting addition product is a viscous, yellow liquid.

This product is epoxidized as follows: 1,150 parts of benzene and 20 parts of sodium acetate are added and heated to 35° C., and then 384 parts of peracetic acid (43.5 percent ig) are added over the course of 20 minutes. The temperature is then maintained for 2 and 2 hours at 35° C.

After this time, it has the theoretical amount

oxidizer reacted. One washes,

neutralizes and then concentrates

a final temperature of 115° C below 0.1 mm Hg. 458 parts of a viscous, yellow liquid with an epoxide content of 3.64 epoxide equivalents/kg are obtained. This product is cured for 24 hours at 140° C with phthalic anhydride (0.7 equivalent anhydride groups per equivalent epoxide group). A bright, yellow, flexible and infusible resin is obtained.

Example 26.

A mixture of 22.5 parts of water and 450 parts of the acetal of acrolein and 1,1-bis-[oxymethyl]-cyclohexene-3 described in example 1 (a) is heated to 80° C. Then 3.5 parts are added p-toluenesulfonic acid, after which a slight rise in temperature takes place and the reaction mixture begins to boil with reflux cooling. The boiling point rises gradually and after 5 hours reaches 90° C, and the bath temperature then amounts to 102° C. At this point, the majority of the water has reacted. One then adds 5 parts Na2CO.„ to neutralize the acid and then distills from 3 parts water and 4 parts unreacted acetal. 461 parts of bis-[2-(2',4'-dioxospiro-5',5'-undecen-9'yl-3')-ethyl]-ether remain in the form of a dark oil. The determination of the double bonds by hydration gives 98.5 per cent of the theoretical.

566 parts of the unsaturated ether acetal obtained are taken up in 1530 parts of benzene, 35 parts of sodium acetate are added and the mixture is heated to 35° C. Then, 580 parts of peracetic acid (43.2 percent ig) are added for 30 minutes. The temperature is still maintained for 2 1/2 hours at 35° C, first by cooling and then by heating. The aqueous layer is separated and the benzoic layer is washed, neutralized and condensed, as described in example 1. Thus, 420 parts of a yellow, highly viscous product with 4.40 epoxide equivalents/kg are obtained, which mainly consists of the diepoxide with the formula

This product gives, after curing with phthalic anhydride (0.6 equivalents of anhydride groups per equivalent of epoxide groups) for 24 hours at 170° C, a bright, infusible resin with very good mechanical properties.

Example 27.

A mixture consisting of 90 parts of 3-vinyl-2,4-dioxospiro (1,5,5)-undecene-9 (acetal of A'-cyclohexene-1,1-dimethanol and acrolein), 90 parts of Diels-Alder- the adduct of 1,4-butanediol to hexachlorocyclopentadiene and 0.5 parts by volume of concentrated sulfuric acid for 4 hours at 80° C. The solid Diels-Alder adduct thereby slowly dissolves. After completion of the reaction, a highly viscous liquid is obtained, which no longer contains any starting material.

The product thus obtained is dissolved in 430 parts of benzene and then epoxidized at 35° C., as described in the preceding examples, after the addition of 5 parts of anhydrous sodium acetate, with 87 parts of 43.6 percent peracetic acid. The reaction duration is 3 hours at 35° C. The processing of the oxidized reaction product takes place analogously to what is described in the preceding examples. You thus finally get 152 parts of a cold-crystallized product with 2.1 epoxide equivalents/kg, which mainly consists of the diepoxide with the formula

The product can be cured with acid anhydrides, such as phthalic anhydride, into very difficult or non-flammable cast objects.

Example 28.

A mixture of 630 parts of 3-vinyl-2,4-dioxospiro(5,5)-undecene-9, 434 parts of ethylene glycol and 4 parts of p-toluenesulfonic acid is heated for 90 minutes to 90° C. The acid is then cooled and neutralized with 5 parts of anhydrous Na«CO:1 and subject the reaction product to a fractional distillation. At 0.15 mm Hg, 52-94° C, 260 parts of unreacted ethylene glycol are obtained, at 0.15 mm Hg, 125-130° C, 500 parts of unsaturated alcohol (3-oxyethoxyethyl-2,4-dioxospiro-( 5,5)-undecene-9 and as a residue 230 parts of the addition product of 2 mol of acetal to 1 mol of ethylene glycol.

The unsaturated alcohol obtained is transferred as follows to the corresponding chlorohydrin.

363 parts of the above-described 3-oxyethoxyethyl-2,4-dioxo-spiro(5,5)-undecene-9 and 1 part of 40% BFs etherate are heated to 80° C. The well-stirred mixture is then added dropwise within 15 minutes 153 parts of epichlorohydrin, if necessary during cooling, ensuring that the temperature is kept at 80-85° C. Then stirring for a further 30 minutes at the same temperature. After this time, any unconverted starting substances can no longer be detected. You thus get 515 parts of a viscous yellow liquid. The obtained chlorohydrin is epoxidized as follows: The obtained 515 parts of chlorohydrin are dissolved in 1390 parts of benzene, 20 parts of anhydrous sodium acetate are added and 219 parts of 43.2% peracetic acid are added dropwise within 30 minutes while cooling at 35° C. You then stir for another 3 hours. The aqueous layer is then separated, the organic phase is washed and neutralized and the solvent is evaporated analogously to what is described in the preceding examples. You thus get 486 parts of a yellow viscous liquid with an epoxide content of 2.63 epoxide equivalents/kg (92 per cent of the theoretical).

The reaction product obtained is then dehydrohalogenated as follows: 479 parts of the epoxidized product is vigorously stirred with 365 parts 30 pst.-ig caustic soda ill/2 hours at 50-55° C. 800 parts of benzene are then added, separated from the aqueous layer and the benzene is distilled off under reduced pressure from the organic layer, increasing the vacuum to 0.1 mm Hg at 100° C sump temperature. You thus finally get 403 parts of a pale yellow thin liquid product with an epoxide content of 5.5 epoxide equivalents/kg (86.5 percent of the theoretical), which mainly consists of the diepoxide with the formula

Claims (6)

1. Process for the production of acetals which are suitable as components for lamination resins, coating compounds, varnishes, dipping resins, casting resins, putty compounds, pressing compounds or adhesives, and which contain at least two epoxy groups, and which have the formula in which X, and X~ mean hydrogen atoms or methyl groups, Z means an epoxyalkyl radical or glycidyloxyalkyl radical, a radical of the formula in which R, - R» means hydrogen atoms, halogen atoms or lower alkyl radicals, since R, and R-, together can also mean a methylene group, the residue of formula or a residue of formula in which X;, and X, means hydrogen atoms or methyl groups, R' , - R'„ hydrogen atoms, halogen atoms or lower alkyl residues, as 5', and R'.-, together can also mean a methylene group, G means the residue obtained by splitting off both hydroxyl groups of a saturated aliphatic or cycloaliphatic diol or polyalkylene glycol or the residue with formula and p means an integer with a value of 1 or 2, n means an integer with a value from 1 to 3 and Y means when n = 1, a remainder of formula in which R"n - R"8 mean hydrogen atoms, halogen atoms or lower alkyl radicals, since R" and R"5 together can also mean a methylene group, when n is greater than 1, the residue obtained by separation of 4-6 hydroxyl groups from a saturated aliphatic polyalcohol with 4-6 hydroxyl groups, characterized by treating acetals which contain at least one epoxidizable group, and which have the formula in which X„ X., and n has the meaning given above, Z' means the residue with the formula in which Hal = bromine or chlorine, a residue of the formula an alkyl residue, a residue of formula in which the symbols R, - R" have the same meaning as above, the residue of formula or a residue of formula in which the symbols X:, and X„ R', - R's, G and p have the same meaning as above, and Y' means when n = 1, a residue of formula in which R"i - R"8 has the same meaning as above, when n is greater than 1, the same residue as Y, with epoxidizing agents. 2. Method according to claim 1, characterized in that one starts from acetals with the general formula in which X2 means a hydrogen atom or a methyl group, and R and R" mean a hydrogen atom or a lower alkyl residue. j 3. Method according to claim 1, characterized by starting from acetals with the formula in which X2 and R" have the same meaning as in claim 2. 4. Method according to claim 1, characterized in that one goes out from acetals of the general formula in which X, means hydrogen atoms or methyl groups, and R means hydrogen atoms or lower alkyl residues, and A' means a tetravalent, saturated, aliphatic, possibly with no more than two hydroxyl groups substituted hydrocarbon residue, which contains 4-6 carbon atoms, and which does not contain any carbon atoms with more than a single free valence, since no hydroxyl groups are further attached to carbon atoms with such a free valence. 5. Process according to claim 1, characterized in that one starts from acetals with the general formula in which X means hydrogen atom or methyl groups and R means hydrogen atoms or lower alkyl residues and A" means a hexavalent, saturated aliphatic hydrocarbon residue, which contains 6 carbon atoms , and which not contains some carbon atoms with more than a single free valence. 6. Method according to claim 1, characterized in that one goes out from acetals of the formula in which the residues X2, X», R" and G have the same meaning as in claim 1, and p means an integer with a value of 1 or 2.