DE1443230A1 - New acetals containing epoxy groups and processes for their manufacture - Google Patents

Description

Or. F. ZmMr - Dr. E Ammom

Dr. K. III D%> Lniys.i.HoUMiNr 144323Ö

New complete registration documents

P 14 43 230.5 Case 4372/1 + 2 / B

CIBA AKiIBHGESEIiLSCiHAi ¹ T, Basel (sweat)

leue epoxy-containing aoetals and Process for their manufacture

The invention relates to new, at least two epoxy groups containing acetals and a process in their manufacture. (

They invented new, at least two epoxy groups Aoetals have the general fosael: BAD ORIGJNAU

New Untejtoe ^ ym, 809806/0798

CK Ni - Q -

(D

, R_, Rg and R for Wasöerstoffatoiae or monovalent substituents such as halogen atoms, alkoxy groups or aliphatic ^, cycloaliphatic, araliphatic or aromatic hydrocarbon radicals, where R ₁ and R _r can also mean an Älkylenreet such as a methylene group, Z a trivalent aliphatic, e-aliphatic or araliphatic hydrocarbon radical with at least 3 carbon atoms and which radical 2 has no carbon atoms with more than a single free valence, furthermore no hydroxyl groups are bonded to carbon atoms with such a free valence, Q for a group

N: -

Nb

or

8 divides, η for a small whole number and Y for an aliphatic, cycloaliphatic, araliphatic or aromatic Best stands with η free valences, where, when n> * l, the Üest Y must contain at least one epoxy group & £.

809806/0798

The acetals containing epoxy groups according to the invention are obtained by adding unsaturated acetals of the general formula

O-

Q -

XTN

Ϊ ¹ (II)

and R _g , Z, Q and η

where R ₁ , R _a , R-, Ri ₁ , R-, R _fi , R-, the same meaning as in formula (X) and Y ^{1 stands} for "an aliphatic, cycloaliphatic !!, arallphatic or aromatic radical, where, if η · 1 lit, the remainder Y * at least. an epoxidizable group or an intoxicating group contain Hues, treated with epoxidizing agents.

Under the term "epoxidizable group" are intended Firstly, residues with epoxidizable C «C double bonds will stand vtro, like an AllyIre» t, $ in ButβnyIreat or a co Tttrahydrobenzylreit; through the influence of e.g. organic

ο,.

^ Peracids leave such 4 # «C double bonds to the 1,2-epoxy

-j group epoxy the re s.

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The term "epoxidizable group" is intended to include furthermore also radicals with a halohydrin grouping

■ ι ι.

- c - c - ■ · ■;. ·

HO shark

(Hal - Haiogehatem) fall, like a P-methyl-glycerin-e-raono »chlorohydrin residue or an illycerin-a-monochlorohydrin residue. Known las3t verifiable such a halohydrin by! Treatment with dehydrohalogenlerenden agents also elm 1,2-Epoxydgrupp® About carts "

The starting materials of the formula (XX} can be obtained, for example, using an aldehyde of the formula in the first “ηΐ”

(XIX)

with a foly alcohol of the formula

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80980G / Q798 '

acetalized. The third functional group O ¹ in the polyalcohol (XV) is preferably also a hydroxyl group, but it can also represent a halogen atom such as chlorine or bromine or a group

- C - 0 - A ₁

stand, where A. is a hydrogen atom or a lower one Alltylrest stands.

Forael aldehydes (IXI) are derivatives of tetrahydrobenzene. Mentioned may be Δ, tetrahydrobenzaldehyde, S-methyl and the like. -tetrahydrobenzaldehyde and 2,5-endoroethylene- ^ -Setrahydrofeenzaldehyde.

Possible polyalcohols of the formula (IV) are: triols, such as glycerol, trimethylolethane, trimethylolpropane, Butanetriol, 2,4j), 1,2,6-hexanetriol, 2,4-dioxy-3-oxymethylpentane; Halohydrins, such as glycerine - «- monochlorohydrin, Olycerin-ß-chlorohydrin, Glyoerln-ii-bromhydrlrt, glyceric acid.

The acetalization can be known per se Methods take place, such as by heating the aldehydes of the formula (III) together with the di- or polyalcohol (IV) in Presence of an acidic catalyst such as hydrochloric acid or p-toluenesulfonic acid.

; * ·; 809806/0798

BATH

You can also use 1 mole of an aldehyde of the formula (ZZZ) to 1 mole of an epoxy of the formula

attach. In both cases one arrives at acetals formula

(VI)

The conversion of the compound (VZ) into the unsaturated acetals of the formula (ZZ) directs the type of functional group Q ¹ . Condensation, such as etherification, esterification or transesterification, with reactive compounds which, for example, contain several mobile halogen atoms or groups containing active hydrogen atoms, is possible, and furthermore the addition of α, α-unsaturated compounds , with one or more. S * S double bonds.

A basic distinction must be made between two cases: BATH ORIGINAL

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• *

The reactive compound used, which is reacted with the acetal (Yl) »contains a Bpoxydgruppe or an epoxidizable group, z _o B« an epoxidizable C «O-Dappel bond, which is not in the reaction with the acetal (VX) reacts · In this case, reactive compounds can be used

with' a reactive group «such as a mobile one Halogenatoo, a hydroxyl or carboxyl group may be used · 2 · The reactive previous training used does not contain epoxy groups bsw · epoxydierbaren groups that do not react at the ready Uwaetzung with the acetal (YI) ₉ In dieaom Pail muQLen the reaktlonefShigain. Compounds at least two reactive groups such as E ₀ B ₀ mobile halogen atoms, hydroxyl, carboxyl groups or for attachment to hydroxyl groups eto. have capable olefinic CeO double bonds.

In case 1, selenium containing all epoxy groups or all epoxidizable compounds from a reactive group as defined above mentioned: pihalohydrins, such as epicblorhydrins, dihelohydrins, such as glycerine chlorohydrins; ungsa ^ -ttigte alcohols such as allyl alcohol, α -Tetrahydrobeneylalkohol and 6-methyl-A -, tetrahydrobenaylalkoholi Glyoerlndiester of unsaturated fatty _# »acids such as Glycerindloleat or unsaturated Glycerindillnoleati Carboneäuren and their functional derivatives such as ^ -TetrahydrobonaoeeUure, 6-mothyl-A -tetraljyclrobenzosBäure, Oelsäuro, JSlaidineäurft, RlolnoleUure "XtlnoXa & ure, Rlclnensäure, etc Xallölsäuren" 3oyafettsäuron _r linseed β CDCR "n, Tungölsliuren, crotonic acid, acrylic acid, methacrylic acid, Aorylsäuremethylester, Acrylylohlorid .;

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unsaturated halides such as allyl bromide and allyl chloride; unsaturated Acetals, such as 3-vinyl-2,4-dioxospiro (5,5) -undeoon-9 and 3-prope? Iyl-

7-mothyl-2 "4-dioxoopiro" (5 "5) -undeeen-9o

In the case of 2 _e , saturated or unsaturated compounds with at least two reactive groups as defined above may be mentioned: saturated polyalcohols, such as ethylene glycol, diethylene glycol, triethyleisglycol, 1,4-butanediol glycerol, sorbitol, pentaerythritol, unsaturated polyalcohols such as Buion42 ^ diol , 4 »!, L-bis & oxymethyl ·} cycloh © ien-3 and l _t l-bis | 'O3! Ymethyl'} 6-m0tl) yl-» cyclohexea «-3» (Klycorlnmonoester urigeoaturated PettsäursfiiWi © ^ lycerin molaoltate or CQycerinmonolinoleaoltat, Dj.- and polyphenols, wi © R © & or @ in, Hyüroquinone, Bie ^ p-oxypheny! ^ Methane and 2.2 «Bistp» oxyphenyl4pTOpe% EohlensMuro, phosgene and polycarboxylic acids, such as Qxaleäura, succinic acid, Mipinsäur®, sebaoic acid _c hexahydrophthalic, Pfethalöäur © »terephthalic acid, Maleiaeäure, i'tuaaröUuTSs? f © trabydrophthalaäur.i, Byros @ llitsäure and their functional!" S @ rivat®, wi © Säurehelogsnide and SäuraanhydridQe 'Further? olyhalogen.verbifidunj>) ny such Biöhlorsethga _f Dichloi ? -

äthan, BibroMäthan _s Biuhl @ rbiit # n ate. W®smv ferbisdungen with awe! oä9T ffl © hs '' C "C-BoppolMstdmngeii that s _o i _s guy lnlaganmg'an" OH groups to form a Ä @ therbrüe CÖ enables EIMD _f such as ethylene glycol - up · ae] ylsäure®et © ir _f? H, N-Bio £ acrylamide ^ methane uad S ₉ M *, N "« -Sriaorylyl-hejahydrsfcffiazin-lä,?,?!

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of acrolein, such as 3,9-divinyl-spirobi- (m-dioxane).

You can also by Acetallsierung of 2 mol Aldehyde of the formula (IXZ) with 1 mol of a polyalcohol of the

Formula '">.. ·

JM - ö - Z ^ (VII)

get directly to unsaturated acetals of the formula (II); as examples of polyalcohols (VII) diglycerin or '

Called acetylene glycol dlglycerln & ther.

Finally, it is also possible to produce directly unsaturated acetals of the formula (IX) by adding 1 mol of an aldehyde of the formula (ZIX) with 1 mol of tin ·· PiaikohoU of the formula

HO.

- 0 - Y «(VIII)

acetalized, the Reot Y 'containing an epoxidizable group. The following may be mentioned as falling games for dialcohols (VIII): Adducts of trios, such as olympics, with Dloyclopentadiene; Diele-Aide; - Adducts of the monoallyl ethers of triols, such as QlyoerjLn ■ «ono-alJylather _# aa cyclopentadiene.

In the method according to the invention, the acetals of formula (II) treated with epoxidizing gowns.

The Bpoxidation of the CC double bonds to the opposite & esen compounds takes place according to customary methods, preferably with the help of organic peracids such as peracetic acid

x. · ■ BAD ORIGINAL

101800/0 ^ 98

- ίο -

acid, perbenzoic acid. Feradipic acid, monoper ph thai acid etc. Hypochlorous acid can also be used as an epoxidizing agent, with KOCL being added to the double bond in a first stage and below it in a second stage Exposure to agents that split off HCl, e.g. strong alkalis, the epoxy group is created.

In accordance with the above about the meaning of the term "epoxidizable group" includes what is said erflndungjogernaaae treatment with epoxidizing agents too the action of agents that split off hydrogen halide, such as potassium hydroxide or sodium hydroxide, on halohydrin groups, e.g. the glycerol monochlorohydrin group, with formation the corresponding 1,2-epoxy group bsw. a Qlycldy! group.

If the acetals of the formula (IZ) contain, in addition to epoxidizable C «C double bonds, also Kalogenhydrlngruppen, the epoxidation takes place in two stages.

In the case of epoxidation, in addition to the di »or« polyepoxides, as a result of side reactions, wholly or only partially hydrolyzed. Epoxides are formed, i.e. compounds in which the epoxy group of the polyepoxide of the formula (I) is entirely or has been partially saponified to hydroxyl groups.

It was found that the presence of such byproducts increased the technical properties of the hardened As a rule, polyepoxides have a beneficial effect. Therefore recommends

BATH ORIGINAL

80 9 80 6 / 0.7 98

-lie "ioh in general, on" ine isolation of the pure
To avoid polyepoxides from the reaction chemistry.

Particularly favorable technical properties
have, for example, the diepoxides of the formula

-CH ₂ - -O- - —C - 0- n-1 OH ₂ . -CH < P. CH - -CH ₀ MM K- ² -

(IX)

where R and R * stand for oxygen atoms or lower alkyl radicals with 1- ^ C atoms, Y _{1 is} an aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radical and m and η are integers with a value of 1 or 2, furthermore the diepoxides Formula.

η-r

-CH

. o-c -

(X)

wherein R and R ¹ FTIR Waesiratoffatom or low · Alkylriste old 1-4 C Atomn! share.

Soloh «Epoicyd« put light, at room temperature
liquid or meltable resins that are calibrated with suitable

■ ORIGINAL BATHROOM

808B06 / 079J3

- 3.2 -

Hardeners, such as dicarboxylic anhydrides ^ in clear and light-colored Transfer hardened products with excellent technical properties.

The epoxidized acetals according to the invention react with the usual hardeners for epoxy compounds. They can therefore be borrowed by adding such substances in the same way as other polyfunctional epoxy ». ^{Crosslink or harden r} '2rb5,' idungen or epoxy resins. Suitable hardeners are basic or, in particular, acidic compounds,

The following have proven to be suitable: amines or amides, such as aliphatic and aromatic primary, secondary and tertiary Amines «e.g. mono-, di» and tributylamines, p-phenyltndiamine, Qia / p-aminophenyl ^ methane, ethylenediamine, Ν, Ν-diethylethylenediamine, diethylenetriamine, tetra ^ pxyäthyl / Tdläthylenetrlamine, Triethylenetetramine, tetraethylenepentamine, Ν, Ν-dimethylpropylenediamine, trymsthylamine, diethylamine, triethanolamine, Mannich bases, piperidine, piperazine, quanidine and guanidine derivatives * Never PhenyIdiguanidin, Diphenylguanidin, Dicyandiamid, Anllinformaldehyde resin, urea-formaldehyde resin ©, Melaraln-formaldehyde resin, polymers of aminostyrenes, polyamides, e.g. those from aliphatic polyamines and di- or trimeric, un-. saturated fatty acids, isocyanates, isothiocyanates; multi-valued Phenols, e.g. resorcinol, hydroquinone, bis ^ T-oxyphenylJfaimethyl-

methane, quinone, phenol aldehyde resins, oil-modified phenol aldehyde

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Resins, reaction products of Alurainiumalkoholaten or -phenolaten with Tautoaier reacting compounds of the Aceteseigester type, Friedel-Crafts catalysts, eg AlCl ,, SbCl ₅ , SnCl ^, ZnCi, BP, and their complexes with organic compounds, metal fluoroborates, phosphoric acid. Preferably used as the hardener lAehrbaaleche carboxylic acids and their anhydrides, for example phthalic anhydride, Hethylendomethylentetrahydrophthalaäureanhydrid, Dodecenylberns teinoäureanhydrid, Hexahydrophthaisäureanhydrid, Hexaehlorendooiethylentetrahydrophthalsäureanhydrid or Endoiwthylentetrahydrophthaleäureanhydrid or their Gemischej maleic oder.Bernsteinsäureanhydridj can optionally B ^ eohleuniger, Hie tertiary · anint get or starch Lewis bases. «.B; Use alkali alcoholates, also advantageously polyhydroxy compounds such as hexanetriol, glycerol.

It has been found that curing the epoxy resins according to the invention with carboxylic acid anhydrides is advantageous 1 Qrmmnequivalent Bpoxydgruppen only about 0 ,? up to 0.9 gram »- equivalent · anhydride groups -used. Bsi application of basic acid accelerators, such as alkali alcoholates or alkali salts of carboxylic acids, anhydride groups of up to 1.0 orcun equivalent can be used.

The term "hardening" as it is used below, means the conversion of the above epoxy compounds to insoluble and infusible resins.

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The present invention therefore relates to auoh curable mixtures which epoxidized the erfindungs.sjemäaaen Aoetals and also hardeners for epoxy resins, such as preferably Oi- or polycarboxylic acid anhydrides.

The curable compositions according to the invention also advantageously contain a proportion of the otherwise corresponding acetals, but all or some of their epoxy groups. Hydroxyl groups and / or other crosslinking polyhydroxy compounds, such as hexanetriol. Of course, other epoxides can also be added to the curable epoxy compounds, such as mono- or polyglycidyl ethers of mono- or polyalcohols, such as butyl alcohol, 1,4-butanediol or glycerine, or of mono- or polyphenols such as resorcinol, bis ^? -oxyphenyl] dimethylmethane or condensation products of aldehydes with phenols (novolaks), also polyglycidyl esters of polycarboxylic acids, such as phthalic acid, and also aminopolyepoxides, such as are obtained, for example, by dehydrohalogenation of reaction products from epihalohydrins and primary or secondary amines butylamine, aniline or ¹ 4, V-di "(monomethylamlno) -diph @ nylmethan.

The hardenable spoxyd compounds or their mixtures Nlt hardeners can also be used in any phase prior to hardening • old fillers, plasticizers, coloring substances etc. added

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will. Ala extenders and fillers can for example Asphalt, bitumen, glass fibers, oil always, quartz powder, cellulose, Kaolin, finely divided silica (AEROSXL) or metal powder can be used.

The mixtures of the epoxy compounds and hardeners according to the invention can be filled or unfilled State, possibly in the form of solutions or emulsions, as textile auxiliaries, lamination resin, paints, varnishes, Dipping hares, Qie3sharze, spreading, filling and leveling compounds, Adhesives, Presemaeson and the like, as well as for the production of such Serving means. The new resins are particularly valuable as xsolatlon compounds for the electrical industry.

In the following, parts mean parts by weight and percentages Weight percent; the ratio of the parts to Sen Dividing by volume is the same as the kilogram to the liter; the Temperatures are given in degrees Celsius.

Representation of the intermediate products.

3 -Tetrahydrobenzal-glycerin.

184 parts of glycerin, 220 parts of Δ'-tetrahydrobenzaldehyde. and 4 parts of p-toluenesulfonic acid are dissolved in 300 parts by volume of benzene and the mixture is heated in a circulation distillation (description of the apparatus in Batzer and coworkers, Makroaolekulare Chemie 1, 1931, 82}) for about 20 hours

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bio 25 parts by volume of water are separated} the rest of the reaction water is absorbed in the desiccant. The cooled solution is shaken first with 100 parts by volume of water, then with 50 parts by volume of soda solution, _{dried with Na 2} SO ^ · and the benzene evaporated. The residue is fractionally distilled. A yield of 290 parts of main fraction (corresponding to 75% of theory) with a boiling point of 98-100 ° ^C. at 0.4 mm Hg is obtained,

This product is catalytically hydrogenated by acid characterization and the hydroxyls & hl determines OH number «263, double bonds« 5.7 equivalentsrsfe® (theory for the connection of the gross formula ^c i ₀ \ ^ ^ö y OH «number ■ 308, double bonds« 5 * 5) ·

Exactly the same as described above, leave below Use of equivalent M @ iig @ n follow © 'Aldehyd® and triols to cyclic acetals *! condensing

^ tf; ferahydrob © nzal "gly certo.

.Acetals ^G lAö ⁰ 3

Acetal sub

Bp approx. 100 ^Θ / 0.4 mmHg

calculated ϋ 66.64 kl found jp 66 _S 46

“ Tetrahydrobgnz aldefayci

1,2,6-hexanetrolol

Acetals

Sdp, 126-128® / 0.08

calculated! G 68.99 H 9 «80 £ found ι ϋ 69.15 H 10.02 $

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-tetrahyclrobenzal ^ glycerln.

MWMMMMMMMMVMWMMHMMMMlUll MMMMiI

Proceed in the same way as described above and condense equivalent amounts of aldehyde and triol to form the following products?

Acetal from 6 ~ Hethyl-.A -tetrahydrobenzaldehyd and 1,2,4-Butantrlol bp. 1Q3 -105V0,2 mm Hg. ^L

Acetal aua D-methyl -. ^ -Tetrahydrobenzaldehyde +

l _y l _t l-trim6thylolpropane. Bp. 119 - 120 ° / 0.2 mmHg.

In the following working examples, the commercially available peraetic acid used is approx. 42%. In addition to sea acid, it contains approx.% Waseeratoffeuperoxid, 10 ^ Wasοer and \%

Parts of 2,5-endomethylene- tetrahydrobenzaloehyde!

+ 184 parts of Olycerin are in a circulation distillation apparatus -

j in the presence of 500 parts by volume of benzene «1 part of anhydrous * j ·

Sink chloride and 1 part by volume kon «. Phosphoric acid condenses. i 33 parts of water are separated out. The solution is r

nitrated and evaporated. The residue is distilled in a high vacuum Ϊ. 310 parts of the cyclic acetal will be obtained »bp 97-100 ° / 0.04 mmHg. \

3 calculated ί C 67.32 H 8.22 ^ \

found t C 67.18 H 3

Sulfuric acid. Sulfuric acid is used before consumption, if not « *

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other things are maltreated with approx. 2% anhydrous sodium acetate neutralized.

Example 1.

198 parts of o-methyl-A, -te trahydrobenzal-glycerin are added dropwise at 2-10 ° to the solution of ^ 9.5 parts Phosgene given in 800 parts by volume of dry benzene. Man If you warm the chemical to room temperature, filter it Pyridinhydrochlorld and washes the filtrate old in the cold 2-N hydrochloric acid, 2-N sodium hydroxide solution and i-m mononatriuraphosphate solution. The solution is dried over anhydrous sodium sulfate, filtered and evaporated to give the carbonate as highly viscous liquid is obtained.

. ■ I A sample is distilled for analysis. . \

Bp. 216-217 ° / 0.02 <snnHg | n ^ ²⁰ - 1.5003 j ^C 23 ^K 3 * ° 7 iwreohnet »C 65.58 H ö

C 65.12 H 8, O7 #

158 parts of the unsaturated carbonate are dissolved in 675 parts of ethyl acetate. Then l6> Share pereosigoic acid admitted. The mixture is initially cooled, then ( kept at 40 ° by supplying heat. After 5V2 hours the: theoretical amount of peracetic acid consumed. Nan diluted with;

500 parts by volume of "^ ethylbenzene, washes with 2 times 100 parts of water"

and steams in a water jet vacuum with the addition of 2000 volumes j

.- ■ "" ■ - ■ - BAD ORiGINAt - f

809806/0798 '

divide ethylbenzene. As a residue, -sin becomes amorphous resin old received 3 »6O epoxy equivalents / kg.

Example 2. - '

The mixture of 396 parts of 6-methyl- "A" "tetrahydro-

benzal glycerin, 146 parts of oxalic acid »diethyl ester, 2 parts ·

Natriunwrathylat and 500 parts by volume of toluene is-In the oil bath, the j

"should have a temperature of approx. 130 - 150 °, heated. [

The alcohol formed is azeotroped with toluene over a 30 hour

high Raschig column "distilled off. After 9056 the theoretical |

Amount of ethyl alcohol have passed over, the solution is filtered [

iwd evaporated. There · Oxftltt remains tie hoohvinkoee [

Liquid. I. A sample is distilled for analysis t j *

ΟΛ Y.

Sdp. 232 - 235 ° / 0.04 anflgj n _p ^w - 1.5043 \

^C 24 ^H 34 8 calculated: C 63.98 H 7.61 $ ♦ found: C 64.17 H 7.59 # *

36Ο parts of the oxalate are mixed in 1200 parts of vinegar

ester dissolved and with 350 parts of peracetic acid for 4y4 hours

let react. The mixture is cooled to 4600 vol- I

share diluted ethylbenzene, mixed with 2 times 200 parts of water

«Bags and then vacuum evaporated in a water jet. The return '.

otand is 3 hours in a high vacuum at 120 ° from the last ■

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609606/0798

Remnants ^ i> 8u: igamitt'S ^ freed. The product is 2.89 spoxy equivalents / kg.

Bsi snlel Jj.,

The mixture of 297 parts of 6-hydrob * 2n? Al-slycerin _?; 110 parts of adipic acid, 1 part of p-toluenesulfonic acid and 1000 parts by volume of toluene are boiled in a circulating distiller. After 10 hours bind 21 parts of water separated.

The solution is then cooled to> 0 ° and 320 parts of pereacetic acid are added in one hour old portions. Not 2 hours at> 0 ° the theoretical 4 long peracetic acid is used up. The data is washed acid-free with Vlaesgr and 2 ~ n 3 adalos, dried over-sea-free with sodium sulphate, filtered and tapped. Ea leaves a tough short with 5.00 epoxy equivalent @ is / kg.

Mixture WM, 396 parts of 6-methyl-tetra-. hydrober.2al »= gXyceriii _# 100 files bsrnsteinaäureanhydrid, X part p-toauolßulfoaäure and 25Ο parts of ethylbenzene boiled for 20 hours in a circulation distiller. 15 parts of viasssr are deposited ^. .

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The succinic acid ester is epoxidized with 45% parts peracetic acid at JO ° for 3 hours. The solution is rendered acid-free with water and 2N sodium carbonate solution, dried over anhydrous sodium sulfate, filtered and evaporated. A tough resin with <2.21 epoxy valents / kg is obtained. ^:

Example 5 .

36.8 parts of s \ * -Tetrahydrobsnzal-Glycerin are '

400 parts of dry benzene and 20 parts of pyridine are added. Bii y are 23.9 parts under ice-salt cooling

3ebaoins acid dichloride was added dropwise. The on HftwntG-npsratu? ;

Arwärate mixture is washed with 3 times 100 parts of water, |

'Dried over anhydrous sodium sulfate and evaporated. |

Be 51 # Ö part · Sebaeate of tetrahydrobenzal glycerol I

obtain. !

42.5 parts of the above product if ground in 30-3 parts' Rssigester dissolved and mixed with 45 parts of pereetic acid during « Reacted for 6 hours at 40 *. The cooled solution old 6V parts by volume of ethylbenzene is diluted, with 2 times Washed 100 parts of water and then evaporated after the addition of 900 parts by volume of Aethylbsnaol. The last heat, «Solvents are removed!», High vacuum up to 120 °. It will 43 parts of a liquid olefin with 3 * 00 epoxy equivalents received per kg.

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- 22 -

B aj.ap.lal 6.

• χ
92 parts «Δ * - tetröhydrobanzalglycerin are with

5T parts of phthalic anhydride, 1 part of p-toluenesulfoic acid, ? .8O parts by volume of benzene in a U.Tilaufdestillierapparat. Heated to the boil for 5 hours. The solution is diluted with 103 parts by volume ■ of benzene and mixed with 20 parts of sodium acetate. Under the cavity, parts are loose within JO minutes Pereasiga acid added. The mixture leaves while stirring React for an hour at 30 °. The LiSaung is -nit 2 times 200 parts; * - 'water and 2 mil 40 parts by volume of saturated soda solution (up to alkaline) and washed over again with 50 parts of water Sodium sulphate, dried and evaporated, remains «In viscous resin with 3 * 5 spoxy equivalents / kg.

Example 7 * '

The mixture of 59 parts of 6-M-sthyl- ^ -tstra- j

• · »i

hydrobenzal glycerin, 420 parts .Ä -Tetrahydrobsnzoic acid »ί

* ι

aiethyleater and 21 parts Natriu.n-niethylatlösu? i3 (2 parts i ^ iV triu-a nad 19 parts "sthanol) is in the α Oalbad" 150 l6O ^c 'is erhitsir The Mithanoi formed on a 30 cm high column Raeehig distilled off. When the distillation stops, 500 parts by volume of toluene are added. The entire distillate contains the theoretical amount of methanol.

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. - 23 -

The mixture is filtered and distilled after cooling down. ^ 3t -Tetrahydrabenosafclureester formed boils bsi

155-158 ^e / 0.2

4jJ2 parts of the above ester are dissolved in 1000 Voluntellen benzene and 60 parts of anhydrous sodium acetate are added. With stirring and cooling, 600 parts of 44.6% pereasiga acid are added over 40 minutes at a temperature of> 0 °. After the mixture has reacted for about 5 hours ivsi> 3 °, the mixture is cooled and washed 3 times with 350 parts of Eievraaser and twice with> 00 parts by volume of 2N soda solution. The aqueous parts "earth" with 600 parts by volume of B-snzol extracted. X> le solution 4β> 3 "p ^ xyde is dried over nitrate sulphate, filtered and evaporated. 429 parts of a liquid, colorless product with 5.02 spoxy equivalents / kg are obtained.

Eg lepieI 8.

49.5 parts of 6-methyl-.Δ * -tetrahydrobenzal-glycerol are mixed with 500 parts by volume of rock-in-oil and 2 parts of pyridine. At 0 °, 50.7 parts of undecylenic acid chloride are added while cooling with Clause. The mixture, warmed to room temperature, is filtered. The filtrate is washed with 200 parts by volume of 2N hydrochloric acid, 200 parts by volume of 2N soda solution and 100 parts by volume of 1M sodium phosphate solution and evaporated. B-Bi of the distillation of the RUckatandee is obtained at 160-162 ° / 0.02 mmHg the undecylenic acid ester of

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3
«Tetrahydrobenzal glycerol as

colorless OsI. n _ß 20 * »1

C ₂₂ H, ^ b 'Calculates :. C - 72.49 H 9,

found ·, C 72.53 H 10,

^ SO Part® of the Undeoylen-sSureeater become with

235 T @ iXen Bsslgsesfcer sand 60 parts of ice Peressigsäare irerinisehl You can read the Ssmiaeh 14 hours to 49 ° anü J hours to about 5 @ ³ reacters. UiQh this tent is the theoretical amount of pereeeigeäurs consumed »Dl © Löaurig is 500

len- aefctiylbtn ^ ©! diluted ni.lt 2 times 150 parts of washed -ίώο siaeh. ^ uaats from. ^ shmals 25Ö ^'7 Olmai-Aethylbäneol in WfiBseretpahlvekuun "liigod & sipft. It is also available with low-viscosity Olepowü

To »i © J? Mixture of 5 · 5 ₉ 8 parts of Δ'-fetra »*

ßjj 0? rush? yridin be Vsi "3 ° βθ _# 2 parts Oleinsäureshlorlä portions gngegeb © a ₉ A ^ schlieseendi ertfärait 'nan on E & y.mtemperstur., mixing the Lösimg ester dso formed nlt 4 eel 100 parts of water ₉ ure" stonet iibsr anhydrous sodium sulphate, filtered off. 41s bus k

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beniylglyoerins obtained.

75f 4 parts of the blasphemous obtained are with 300 parts Weirdest mixed up. 110 parts of peracetic acid are added in portions to the mixture in 1/2 hour. Leave for 3 hours 40 ° react. The solution is with 400 parts by volume of ethylbenzene diluted, washed twice 100 parts of water and evaporated with the addition of another 800 parts by volume of ethylbenzene. The residue was a liquid epoxide with 3 # 92 poxide equivalents / kg obtain.

Example 10

462 parts of chlorohydrin are added dropwise to a mixture, heated to 55 °, of .921 parts of δ-tetrahydrobanzal glycol and 5 parts by volume of 48% boron trifluoride in ether. The mixture is then allowed to cool to room temperature and neutralized with 1.8 parts of powdered sodium hydroxide solution (an identical reaction product is obtained if 1 pint of spichlorohydrin is first condensed with 1 pint of glycerol, and then the oleic monochlorohydrin ether obtained is condensed with Δ, -totrahydrobenzaldehyde acetal ! - eggs). *

1100 parts of feracetic acid are slowly added to the entire reaction product dissolved in 2500 parts of üssigostar. Bach 6 hours at 30 °, the theoretical amount of peracetic acid is consumed. The solution is diluted with 2,000 parts by volume ethylbenzene _c washed with 1,500 parts of water and evaporated in tfasserstrahivakuum under Zusats of 3000 Volumteilon ethylbenzene one "is obtained old fipoxydäquivalentβ 2.64 / kg product.

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.. 26 -

1200 parts of the above monoepoxy are with

2000 parts by volume of dry benzene mixed and cooled up to 20-25 ° with 165 parts of finely powdered sodium hydroxide added «Another 1 hour is filtered off from the sodium chloride formed. The filtrate is 230 parts by volume of 1 m monosodium phosphate solution washed, dried over sodium sulfate, filtered and evaporated. It becomes a liquid diepoxyd with 5.56 epoxy equivalents / kg obtained.

• Example 11,

The mixture of 297 parts of O-methyl-.DELTA.-tetrahydrobsnz & l-glycerine, 500 vol. Parts of dry benzene and 1.5 parts by volume of 486 parts of boron trifluoride in ether is heated to 75 °. 139 parts of epichlorohydrin were added dropwise to stoves with stirring. Due to weak cooling HiFd the temperature was not allowed to rise above 81 ° .. After finished? Addition of the epilorhydrin is allowed to cool to room temperature and 60 parts of powdered äm & zn & tzon are added in γ4 hours with stirring. The temperature is kept at a level of 25 ° by cooling. After a further 23 hours the mixture is filtered. The filtrate is evaporated, 0.2 parts by volume of glacial acetic acid are added and the mixture is rapidly distilled (bp 117-1 ^ 2 ° / approx. O. ^ saraHg). The fractional distillation in a Vigreux column provides the olycidyl ether with bp 131-137? / 0.4 amKg. Bas product contains 3.90

BATH ORIGINAL ■

Epoxy equivalents / kg (99 dollars theory). Analysis : ^c i4 ^H 22 ° i »

- calculated: C 66.11 H 8.72 O 25.17 * found: C 66.17 H 8.80 0 25.10 *

178 parts of the above olycidyl ether are mixed with 500 Diluted parts by volume of benzene and admixed with 15 parts of anhydrous sodium acetate.

With cooling at approx. 30 ° in ^ 2 hours 1 * »5 parts of 44.6% peracetic acid were added in portions. . React for a further 1 hour and 50 minutes at approx. JO * and then cools down. The benzylic solution of the epoxy is Washed 3 times with 200 parts by volume of ice water, 200 parts by volume of 2N Södalöaung and 150 parts by volume of monosodium phate solution. The aqueous parts are extracted with 400 volumes of benzene. The combined benzylic extracts become over anhydrous Dried sodium sulfate, filtered and evaporated. One gets 157 parts of low viscosity diepoxide with 6.5 epoxide equivalents / kg (88 * of theory).

Example 12.

99 parts of the dioxolane obtainable from 1,2,4-ßutantrlol and Δ -tetra-hydrobenzaldehyde are reduced to about 45 ° heated. Ee 0.2 parts by volume about 48 liters of boron trifluoride in ether and added dropwise 46.3 parts of epichlorohyarine.

• BAD ORIGINAL>

• 809806/0798

- 28 -

The temperature is allowed to rise to 83 °. 15 minutes after addition of the offset to Epiehlorhydrins mit.2 parts of anhydrous NatriaTiacetat, diluted with S5O Essigester parts and portions are ill TtIIe peracetic acid to the mixture after * β levels reacted at 40 ^e, is mixed with 200

^ ethylbenzene «jwäünnt, with 2 times 50 parts of water and after additives of 750 folumtailtn Äefchylbenzol evaporated in a water jet vacuum »

The obtained © Kcnoepoxyd is in 250 volume cells Benzene g € ld * sfe and with 20 ssiltn of finely powdered matrium

Measure llseS 2 SfcundeE at 21 «» 2β ^ο respond. The gabäl ^ et® Natrlumohlos ¹ ^ is afefilSriert "the fiItrate is divided into Sq yolum 1-sa SSenonatriuo ^ hosphatlueung g®" wasohen, t! B © 3? w & saerfroieüi KaLuriuaoulfafe getpoetetict «filtered and evaporated, it is obtained @ £ ia liquid diepoxyä with 5 ₉ 86 epexy equivalents / kg. ; #

Example 13 «

im ic in - ^r 'ii Wi ι »Ii - nfimι n imnui.

mm g®MB.u the same as in "Example 12, but the m-dioxane" derivative obtainable on S ^ Hethyl-tetrahydroba ns al de5, yd ynd l _f l _# l "Trioie% hylolpvopan", so .a fltteaigea Oiepoxyd ßit %, ^ 5 Epossrd equivalents / kg.

BATH ORIGINAL

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- 29 -

Example 14.

113 parts of dee from 1,2,6-hexanetriol and Ά -tetrahydrobenzaldehyde available dioxolane are in the presence of 0.3 Completely divide 48% boron trifluoride in ether with 46.3 parts Epichlorohydrin implemented at 70 °.

After cooling, the product is mixed with 2 parts of anhydrous sodium statate and diluted with 300 parts Easigeater. Then 110 parts of peracetic vinegar are added in batches. acid added. The mixture is left at 40 ° for 3 hours react. Nan diluted with 1000 parts by volume of ethylbenzene and washed with 2 times 130 Tillen of water and steamed after repeated Addition of 500 parts by volume of ethylbenzene in a vacuum. That Product is taken up in 500 parts by volume of benzene and mixed with 20 parts of finely powdered sodium hydroxide at 25 ° dehydro » halogenated. The Oemlsoh is filtered. The Piltrat will «Washed with 50 parts by volume of 1 m cononatrium phosphate solution, dried and evaporated. There are 115 parts of liquid Diepoxy obtained with 5.51 epoxy equivalents As *

Example 15,215 parts of distilled diglycerol, 300 parts

-Tetrahydrobenzaldehyde, 750 parts by volume benzene, 3 parts Anhydrous zinc chloride and 3 parts by volume of phosphoric acid are boiled in a circulating distillation apparatus with stirring. To

BATH

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43 parts of Woeser are deposited in 4V2 hours. The mixture is filtered and evaporated, finally in a high vacuum at 120 °. 40 parts of the bis-dioxolane are obtained.

The above dioxolane is dissolved in 1500 VoI lunte Ilen benzene and with 20 parts of anhydrous sodium acetate are added with stirring and * Kühleu in portions over one hour at 30 ° 550 parts 44.6 # peracetic acid added to _r. After the mixture has reacted for another 2 hours at 30 °, it is cooled with ice. The epoxy solution is washed acid-free with 3 times 300 parts of water and 2 times 300 parts by volume of 2N soda solution. The aqueous parts are extracted about 500 parts by volume of benzene. The benzene parts are combined, dried over anhydrous sodium sulfate and evaporated. 399 parts of a viscous Biepoxydff with 4 * 55 epoxy equivalents / kg are obtained.

Example 16. ♦

159 parts of raw diglyoerii? (in a known way from glycerin and olycerin-e-monochlorohydrin in the presence of Sodium hydroxide solution) are mixed with benzene in JOO parts by volume 220 parts .2 ^, ~ tetrahydrobenzaldehyde in the presence of 1 part Zinc chloride and 1 part by volume of concentrated phosphoric acid in one circulation distiller door condensed. There are 29 parts Separated water. ·

BATH ORIGINAL

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The filtered solution of the bis ~ dioxolana is portionenwelae at oa. 420 parts of peracetic acid are added at 20 ° for ¹ 1/2 hours. After the mixture ^{has reacted for 3} Zk hours at 30 °, it is washed free of acid with ice water and 2N soda solution. The solution is dried with anhydrous sodium sulfate, filtered and evaporated. A high-viscosity resin with 4.62 epoxy equivalents / kg is obtained as the residue.

Example 17.

82 parts of distilled diglycerol are in a circulation distillation apparatus with 130 parts of 6-methyl-Z ^. -tetra · hydrobenzaldehyde in the presence of 500 parts by volume of benzene, 0.5 part of zinc chloride and 0.5 parts by volume of phosphoric acid condensed. 15 parts of water are separated off. The solution is filtered and evaporated. The residue is distilled in a high vacuum. 156 parts, Bia-ecetal, bp 189-199 ° / 0.2 mmHg are obtained. _#

141.5 parts of the Bls-acetale are dissolved in 500 parts of Esslgeoter and 165 parts of peresaiga acid are added in portions. The temperature is initially kept at 40 ° by cooling, then by external heat supply. After 1/2 hours, 97 $ of the theoretical amount of peresalgic acid has been consumed. It is cooled, diluted with 500 parts by volume of ethyl benzene, washed with 2 times 150 parts of water and evaporated

BATH ORIGINAL

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Vacuum with the addition of 1000 parts by volume of ethylbenzene. Pie last beds are solvents at 120 ° in a high vacuum removed. There are 143 parts of epoxy resin with 3.75 epoxy equivalents / kg obtain. '. .

Example 18.

The procedure is exactly the same as in Example 17 beschriebena Jedcoh used in place of methyl 6 ~ ».Δ -tetrahydrobenzaldehyds 125 parts of 2-5 _{e-Kndomethylen} .A '- tetrahydrobenzaldehyde. The BIe-acetal obtained boils at 202-204 ° / 0.2 mmHg,

In the case of epoxidation, after 3 hours is the theoretical Amount of pereeeigsäw «consumed» & 8 diepoxyd received is © in ajiorphes, epFööes Harz. The Epexydgehalfc ittesfe itself Cannot determine with broea.

Example 19.

il2 feile @ i ^ eerin «monotri @ yclod @ o @ nyläther '(Adduct from ßl @ yclopent ^ i @ ^% md Olyces ° i ^} are in one- * Umlaufdeatilli @ rappas! afcur In @@ genvi & rt of 0.2 Parts of Sink »chloride j, O ₉ 3 vol quantities, phosphoric acid and 300 vol. Of benzene condensed with 60 parts of tetrahydrobenzaldehyde. Bio solution of the acetal formed is filtered and evaporated. Lev residue is distilled. Parts become Product obtained from ΒύρΛβ5 "112 ^ϋ / 0 _$ Q2 mMg .

I-

^c 20 ^H 28 ° 3 calculated: C 75 _f 91 'H 8

found: C 75.80 U e

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• ■ ■

'- 33 -

11 parts of the above acetal are mixed with 300 parts of ethyl acetate. It is left with 150 parts at 40 ° for 5 hours Peracetic acid react. The mixture is cooled, diluted with 500 parts by volume of ethylbenzene and washed with 2 times 150 parts of water. The solution is added again of 500 parts by volume of ethylbenzene in a water jet vacuum evaporated in a water bath. It becomes a viscous Dlepoxyd with 5.22 epoxy equivalents / kg obtained.

Example 20.

A mixture of 180 parts of 3-vinyl-2,4-dioxoapiro (5.5) undecene-9, which was prepared by aoetallsleren of 4 & k ^ -Cyclonexen ~ l, l ~ dimethanol with acrolein, and 184 parts of ^ X'-tetrahydrobenzalglycerol is heated 80 °. Then 1 part of HgSO ^ is added. A positive heat tone is observed. The temperature is kept at 90 ° for two and a half hours, first by cooling and then by heating. First of all, the acid is mixed with 1 part of anhydrous Ma ₂ CO. neutralized. By heating the reaction product to 112 ° / 0.2 strnHg, only 6 parts of unchanged starting materials can be distilled, ie the addition proceeds almost quantitatively. 353 parts of the adduct remain in the form of a viscous, dark liquid.

353 parts of the addition product described above are dissolved in 1050 parts of benzene. 25 parts of water

\. BATH ORIGINAL

'. 809806/0 * 79.8

free sodium acetate and heated to 35 °. Anachliosaend 394 parts of peracetic acid (4l _p 2 # Lg) are added over 20 minutes with thorough stirring. Daa mixture is stirred at 35 ° a further 2 ^ / k hours. It is then cooled and the aqueous layer is separated off. It is then washed 3 times with 250 parts by volume of water, neutralized with 40 parts by volume of sodium hydroxide solution (30%) and finally washed a further 2 times with 15% by volume of water. The benzene is then distilled off and the product is heated to 100 ° at 0.1 mm in order to remove the last residues of solvent *. In this way 320 parts of a yellow viscous liquid are obtained which contain 4.75 epoxide equivalents / kg (94% of theory) and which are mainly derived from the epoxide formula

OH"

| ^ CH ₂ 0 ^ ² * ^ CH ₂ O- j (

OH «· ■ CH ₀ CH

consists.

Example 21.

65 file of the vegetable Example 3 produced epoxy j

will harna be at 120? with 28.9 parts of phthalic anhydride [

melted and in an aluminum oil si orm (40 χ 10 χ 140 mm): filled in, ■ ·

The mixture is 3 hours at 120 °, 3 hours at ■ Cured 160 ° and 24 hours at 200 °. The body shows

BAD ORIGINAL = - \ 80980 6/0798

following properties *

Flexural strength t 11.6 kg / ma ²

Scfclagbiegef eeti. ability t 13 # 5 kgcm / cm heat resistance after hardening s ¹ ^ ⁰⁰

Example 22

75 ropes of the diepoxyd produced according to Example 7 and 18.8 ropes of succinic anhydride are treated at 120 ° and in an aluminum casting mold (40 χ 10 ζ 140 ajm) filled. ·

The rent is 16 hours at 120 ", 6 hours at 160 * and 32 hours bit 200 * hardened, the oil body obtained Has the following properties

Flexural strength ι 9.0 kg / mm

Bottom bending capacity ι 6.8 kgom / cm Heat resistance at Marten ι 175 °

BATH ORIGINAL

809806 / 079.6

- 36 Example 23

65 parts of the diepoxide prepared according to Example 15 are fused with 28.4 ropes of phthalic anhydride at 120-130 ° and in an aluminum casting mold (40 10 ζ 140 mm). filled

. The smell is hardened for 24 hours at IHO ⁹ and 24 hours at 200 °. The cast body shows the following properties:

Flexural strength. t 10.1 kg / mm impact strength ι 7.9 kgcm / cm heat resistance according to Martens t 187 ^s

Example 24

70 parts of the Example 15 gemäse diepoxide be prepared with 21.2 parts of phthalic anhydride at 120 ° fused · The mixture thus prepared at 120 ° feat a viscosity of 20 * woniger as oP and after $ & minutes such 1500 oP "The melt poured onto Olaa plates in a layer thickness η of V10 and 1 mm and cured for 24 hours at 140 ° and 24 hours at 200 °. The films obtained are clear, "practically undyed, elastic and show very good adhesion to the substrate"; na «sh 1-hour? Effect of 5> -n sulfuric acid, 5-n sodium

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lye, water, acetone, chlorobenzene at room temperature and they remain unchanged «

Example 25

74 parts of the epoxy resin prepared according to Example 16 and 32 # 8 parts of phthalic anhydride are used fused at 120 ° and placed in an aluminum casting safe (40 χ 10 χ 140 mm) filled. -

The mixture is cured at 140 ° for 24 hours. The casting obtained shows the following properties

Flexural strength t 6.1 kg / W

Sole lay strength j 3.8 kgcm / cm Resistance to heat according to Martens t 173 °

Example 26

68.5 parts of that prepared according to Example 10 EpoayharEöt are at 120 ° with 36.5 parts of phthalic anhydride ▼ melted and in an aluminum mold (40 χ 10 χ 10 mm) filled. The mixture is hardened for 4 hours at 80 ° and 24 hours at 140 °. The casting obtained has the following Characteristics:

Flexural strength ι 10.9 kg / mm

Impact bending strength t 12.1 kgcm / cm Martens temperature resistance: 147 °

BAD ORlGlNAt. 809806/0798

Claims (4)

Claims, 1. Process for the production of new acetals containing at least two epoxy groups * the Formula: R. CH Z-G- _t R, R, Rq and R for hydrogen cn o co where R , R, R, atoina or uniform subatifcuents, such as halogen atoms, Alkoxy groups or aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radicals, whereby Methylene group, can mean Z is a trivalent aliphatic, oyoloaliphatic or araliphatic hydrocarbon creature with at least ? C atoms means and which radical Z means no carbon atoms with more than one has a single free valence, furthermore on carbon and R ₁ . together also an Alkylenreat, like one SAD ORfGSNAL New subjects ιαπ7 μλ * 2 νμ Atoms with such a free valence do not have hydroxyl groups are bound, 0 for a group 0, jC »O or * 0 Bteht, η for a small integer and Y for one, aliphatic, cycloaliphatic ^ araliphatic or aromatic radical with 'η free valences, where, if η - 1 1st, the radical Y must contain at least one epoxy group, characterized in that acetals are used general formula O- α - where R ₁ * Rg, R-, R ^, R ₅ , Rg, R «# Rg and R., Z, Q and η have the meaning given above and Y ^{1 is} an aliphatic, oyoloaliphatic, araliphatic or aromatic radical, where, if η - 1, the remainder Y * contains at least one epoxidizable group or one epoxy group nut, old epoxidizing agents are treated. 'BAD ORIGINAL 809806/0798 r-, 2. The method according to claim 1, characterized in that one starts from acetals of the formula H - C
MR .CH. I 2 -CH -i: IH, «0- CK L k 2- ¹ -ο n-1 wherein H and R "atehen for Waeeeretoffatome or lower alkyl groups with X-4-C Ätomen ₀ Y, © inen aliphatic, araliphatic or aromatic hydrocarbon cycloaliphatieahen _s υηύ m and η g & nse numbers with a value of 1 or 2. 3. tf @ i * drive according to s claim I ₉ dad indicated that the assumption is based on Asefealen of the formula Mr -CH, , CH, -0-C-CM IgH
R'-CH CH Krorin R and R «fttr Waaseratoffatome or lower Älicylreste with 1-4 carbon atoms. BATH ORIGINAL 4. New acetals containing at least one protein the formula CH Z -G- wherein R ₁ , Rg, R *, Rj, Rc »Rgi R ^, Hg and Rg for hydrogen atoms or monovalent substituents. such as halogen atoms, alkoxy groups or aliphatic, cycloaliphatic ρ araliphatic ^ or aromatic hydrocarbon radicals, where R and R ₅ together can also mean an alkylene radical, such as a methylene group, Z a trivalent aliphatic, cycloaliphatic or araliphatic hydrocarbon radical with at least 3 * C atoms means and which radical Z has no carbon atoms with more than a single free valence, furthermore no hydroxyl group ^ are bonded to carbon atoms with such a free valence, & AD OBSGINAL 809806/0798 G ffsT a group a O. 0 0, C = O or ^ 0 represents, η stands for an integer and Y ffcr an aliphatic, cycloaliphatic, araliphatic, often aromatic radical with η free valences, where, when η «1, the radical Y must contain at least one epoxy group . BAD ORSGfIMAL 809806/0798