SE180083C1 - - Google Patents

Description

Uppfinnare: H Batzer och 'E Nikles Prioritet begard [ran den 2 april och 23 juli 1958 (Schweiz) FOreliggande uppfinning avser nya, som textilhjalpmedel, lamineringshartser, lacker, gjuthartser, pressmassor, spackelmassor eller bindernedel kvavehaltiga epoxidforeningar med den almanna formeln R, R, \ / RII X ,\C /, I o/ CC—CH, N Ro Rg Ci R7 _R,' R,' Y\ / R.,' .0 \R,' I \/ \/ —[Z]iniN CH,--C C\ 19.8'\C 1717/c/ (I) Ro Ro van iR1'., R25 R215 R35 B-31, R45 R4'5 R55 R5' Rs, 1161, R75 R7t, R8, R8', R, och R,' beteckna lagre alkylrester med 1-4 kolatomer eller vateatomer, varvid R, och Ho respektive R1' och R8' tillsammans aven kunna beteckna en metylengrupp, X och Y beteckna acyl-, karbalkoxi-, karbaminyl-, cyan- eller sulfonylrester, Z beteck- Rot Rot nar en alkylen- eller fenylenrest, m betecknar ett belt tal med ett hogsta vdrde av 2 och n betecknar ett litet, halt tal. Inventors: H Batzer and 'e Nikles Priority requested [April 2 and July 23, 1958 (Switzerland) The present invention relates to novel, such as textile aids, laminating resins, lacquers, casting resins, compacts, putties or binder nitrogen-containing epoxide compounds of the general formula R, R , \ / RII X, \ C /, I o / CC — CH, N Ro Rg Ci R7 _R, 'R,' Y \ / R., '.0 \ R,' I \ / \ / - [Z] iniN CH, - CC \ 19.8 '\ C 1717 / c / (I) Ro Ro van iR1'., R25 R215 R35 B-31, R45 R4'5 R55 R5 'Rs, 1161, R75 R7t, R8, R8' , R 1 and R 2 'represent lower alkyl radicals having 1 to 4 carbon atoms or hydrogen atoms, wherein R 1 and H 2 and R 1' and R 8 'together may also represent a methylene group, X and Y represent acyl, carbalkoxy, carbaminyl, cyano or sulphonyl radicals, Z denotes- Root Rot denotes an alkylene or phenylene radical, m denotes a belt number with a maximum value of 2 and n denotes a small, content number.

De nya foreningarna med fomeln (I) erhallas enligt uppfinningen, om foreningar med den all-manna formeln Ito C G R2 \ C R1 C C—CH,—N pX _Lao /I Rs / r R,' R13' R3:R2' \G/R,' \C/ (II) /\ /\ \ R, R, / \ .1. L7‘1.,R4' R,' R,' van i R,, R1', R25 R215 R35 R3'5 R45 R415 R55 115'5 R„ R8', R„ R7, Ro, Ro', 119, R'9, X, Y, Z, iii. och n ha den ovan angivna betydelsen, epoxideras genom omsattning med epoxiderande medel, sâ- sorn perattiksyra eller perbensoesyra. 2— — UtgangsfOreningarna med formeln (II) kunna a sin sida erhallas, om sekundara aminer med den. allmanna formeln R, RiB2' R, \C/ R, XY\c( R3' \ C—CH,—N— \C/ vanR7, R21, R33 R313 R4, 1R4'7 R51 R71, B.6, R,', R7, R,', R.8, R8', R,', R,,Z,mochnhadeni formeln (I) angivna betydelsen, behandlas med medel, vilka kunna infora en acyl-, karbalkoxi-, karbaminyl-, cyan- eller sulfonylrest. The novel compounds of formula (I) are obtained according to the invention, if compounds of the general formula Ito CG R2 \ C R1 CC — CH, —N pX _Lao / I Rs / r R, 'R13' R3: R2 '\ G / R, '\ C / (II) / \ / \ \ R, R, / \ .1. L7'1., R4 'R,' R, 'of i R ,, R1', R25 R215 R35 R3'5 R45 R415 R55 115'5 R „R8 ', R„ R7, Ro, Ro', 119, R '9, X, Y, Z, iii. and having the meaning given above, is epoxidized by reaction with epoxidizing agents, such as peracetic acid or perbenzoic acid. 2— - The starting compounds of formula (II) may in turn be obtained, if secondary amines with it. general formula R, R 1 B 2 'R, \ C / R, XY \ c (R 3' \ C — CH ', R7, R,', R.8, R8 ', R,', R ,, Z, mochnhaden in the formula (I) indicated or sulfonyl residue.

For inforande av acylresten ifragakomma exempelvis mono- och dikarbonsyror och deras funktionella derivat, sasom syrahalogenider, och foretradesvis syraanhydrider. For the introduction of the acyl residue, for example, mono- and dicarboxylic acids and their functional derivatives, such as acid halides, and preferably acid anhydrides are available.

Den salunda inforda acylresten han utgOras av ,0 en rest med formeln —C" , van A1 betecknar en eventuellt substituerad alifatisk, cykloalifatisk, aralifatisk eller aromatisk kolvaterest eller en heterocyklisk rest; den kan vidare exempelvis 00 motsvara formeln varvid " "OH A2 betecknar en eventuellt med funktionella grupper eller heteroatomer avbruten alifatisk, cykloalifatisk, aralifatisk, aromatisk eller heterocyklisk rest. The acyl residue thus formed is a residue of the formula -C ", van A1 denotes an optionally substituted aliphatic, cycloaliphatic, araliphatic or aromatic piston residue or a heterocyclic residue; it may further, for example, correspond to the formula wherein" "OH A2 optionally interrupted by functional groups or heteroatoms aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical.

Inforandet av en karbalkoxirest kan exempelvis ske med halogenmyrsyraestrar. Karbalko)dresten kan exempelvis motsvara formeln —C-0—A1, 0 van i Ai betecknar en eventuellt substituerad, alifatisk kolvdterest. The introduction of a carbalkoxy residue can take place, for example, with haloformic acid esters. The carbalko) moiety may, for example, correspond to the formula -C-O-A1.0 van in Ai denotes an optionally substituted, aliphatic piston residue.

For infOrande av karbaminylresten kan man _11-1. Rai\ R7/ \\c// \R R,' exempelvis utgâ fran karbamid eller frail en Nsubstituerad karbamid, varvid under avspj älk,A3 fling av NH3 en rest med formeln —C—N, \ 0 infores, varvid A3 och A4 kunna beteckna vateatomer eller alifatiska, cykloalifatiska, aralifatiska, aromatiska eller heterocykliska rester. For introduction of the carbaminyl residue one can _11-1. Rai \ R7 / \\ c // \ RR, 'for example, starting from urea or frail an N-substituted urea, wherein during play, A3 flake of NH3 a residue of the formula -C-N, \ 0 is introduced, whereby A3 and A4 can denote hydrogen atoms or aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radicals.

InfOrandet av cyanrestenkan exem- pelvis ske med en halogencyanid, sasom bromcyan. The cyanide residue can be introduced, for example, with a halogen cyanide, such as bromocyanine.

Inforandet av en sulfonylrest kan exempelvis ske med klorsulfonsyra, halogensvavelsyraestrar eller sulfonsyror eller deras funktionella derivat, sasom. sulfonsyrahalogenider. Sulfonylresten kan exempelvis motsvara formeln 0 \ P van i Ai liar samma betydelse som i acylresten med formeln —C—Ai och p betecknar ett helt tal 0 med ett varde av 1 eller 2. The introduction of a sulfonyl residue can take place, for example, with chlorosulfonic acid, halosulfuric acid esters or sulfonic acids or their functional derivatives, such as. sulfonic acid halides. The sulfonyl radical may, for example, correspond to the formula O

De sekunddra aminerna med formeln (III) kunna framstallas enligt olika forfaranden. The secondary amines of formula (III) can be prepared according to various procedures.

Man kan salunda framstalla sekunddra monoaminer med formeln (IV) R, .R.1R1 R.,' \ / R„c, R,R,' \c/ R3' C C—CH,—NH—CH,—C C .1 R8116' cRi' /\ R61 B.' 114/ \\c/7 \11., (IV) — genom aft underkasta foreningen med formeln R2 R, R3 NG/ R, \/ C—B R, /\ /\ 114 'G R, R R6 van i R„ R,, R3, R., R,, R,, R„ R, och R, ha den ovan angivna betydelsen och B betecknar en envard rest med nagon av formlerna 0 —C,, —CH=NH, \NH, —CH=N—OH och R,' R,' \ R,'CR31 \ \ —CH=N—CH,—C R/ \C/ ,' Tt4' /\ R.'' ,11, eller deras bildningskomponenter en hydrering vid betingelser, vilka icke astadkomma nagon mattning av C = C-dubbelbindningen i cyklohexenringen. There can thus be prepared secondary monoamines of the formula (IV) R, .R.1R1 R., '\ / R „c, R, R,' \ c / R3 'CC — CH, —NH — CH, —CC .1 R8116 'cRi' / \ R61 B. ' 114 / \\ c / 7 \ 11., (IV) - by aft subjecting the compound of the formula R2 R, R3 NG / R, \ / C — BR, / \ / \ 114 'GR, R R6 van i R „R R 3, R 3, R 3, R 3, R 3, R 3, R 3, and R 4 have the meaning given above and B represents a monovalent radical of any of the formulas 0 -C ,, -CH = NH, \ NH, -CH = N — OH and R, 'R,' \ R, 'CR31 \ \ —CH = N — CH, —CR / \ C /,' Tt4 '/ \ R.' ', 11, or their formation components a hydrogenation at conditions which do not cause any matting of the C = C double bond in the cyclohexene ring.

Genom lampligt val av utgangskomponenter kan man erhalla symmetriskt byggda eller ocksa osymmetriskt byggda fOreningar med formeln (IV). By suitable choice of starting components it is possible to obtain symmetrically built or also asymmetrically built compounds of formula (IV).

Man erhaller exempelvis symmetriskt byggda foreningar med formeln (V) R, R,R, R2 R. \ G/ R.R. ,c, R9 \ \C/\ \ C—CH2—NH—CH2—C C (VI) R5 Re R6 R om man hydrerar iminer, oximer, syraamider eller sarskilt nitriler med formeln (V) eller om man utgar frau en schiffsk has med formeln (VII) R2 R,R, R. There are obtained, for example, symmetrically constructed compounds of the formula (V) R, R, R, R2 R. \ G / R.R. , c, R9 \ \ C / \ \ C — CH2 — NH — CH2 — CC (VI) R5 Re R6 R if one hydrates imines, oximes, acid amides or especially nitriles of formula (V) or if one starts from a Schiff of formula (VII) R 2 R, R, R

R3 /C\'3 R, ,c, R3 \/\ /\/ CC—CH =N—CH 2—CC R8 CC R4 "c" R, /\ R R6 (VII) Sadana schiffska baser kunna a sin sida exempelvis erhallas genom kondensation vid reducerande betingelser av 2 mol av en aldehyd med formeln (VIII) med 1 mol ammoniak. Man kan darvid a.ven utan isolering av den intermediart bildade schiffska basen (VII) erhalla foreningen med formeln (VI) direkt genom att underkasta en blandning av 2 mol av fOreningen med formeln (VIII) och cirka 1 mol ammoniak hydrerande betingelser. R3 / C \ '3 R,, c, R3 \ / \ / \ / CC — CH = N — CH 2 — CC R8 CC R4 "c" R, / \ R R6 (VII) Such schiff bases can be on their side for example obtained by condensation under reducing conditions of 2 moles of an aldehyde of formula (VIII) with 1 mole of ammonia. In this case, even without isolation of the intermediate-formed schiff base (VII), the compound of formula (VI) can be obtained directly by subjecting a mixture of 2 moles of the compound of formula (VIII) and about 1 mole of ammonia-hydrogenating conditions.

Man kan vidare erhalla de schiffska ba.serna genom att bringa 1 mol av en amin med formeln — — R, \ / Ra,c \R, C—CH2—NI-12 /11, \ R4 NC/ R, / \ R, att reagera med 1 mol av en aldehyd med formeln (VIII). The Schiff bases can further be obtained by bringing 1 mole of an amine of the formula - - R, \ / Ra, c \ R, C — CH2 — NI-12/11, \ R4 NC / R, / \ R , to react with 1 mole of an aldehyde of formula (VIII).

Sarskilt lattillgangliga aro de sekundara aminerna med formeln CH..CH2 / - \/ \ HC CH—CH2—NH—CH2—CH CH 11i HC CH—RR'—CH CH \/\Lo.± ,..,„. / C I12"2 (X) van i R och R' beteckna en vateatom eller en lagre alkylrest. Particularly readily available are the secondary amines of the formula CH..CH2 / - \ / \ HC CH — CH2 — NH — CH2 — CH CH 11i HC CH — RR' — CH CH \ / \ Lo. ±, .., „. / C I12 "2 (X) van in R and R 'represent a hydrogen atom or a lower alkyl radical.

For framstallning av bis-03-tetrahydrobensy1)- amin kan man utga fran.43-tetrahydrobensonitril, som latt framstalles genom anlagring av akrylnitril vid butadien. For the preparation of bis-3 O-tetrahydrobenzylamine, one can start from 43-tetrahydrobenzonitrile, which is easily prepared by depositing acrylonitrile with butadiene.

Bis- (6 -mety1-.61, -tetrahydrobensyl)-amin kan framstallas utgaende frail ammoniak och 6- metyl-z13-tetrahydrobensaldehyd, varvid den sistnamnda fOreningen ãr latt att framstalla genom anlagring av krotonaldebyd vid butadien. dr vidare bis-(1,5-endometylen-.613-tetrahydrobensyl)-amin. Bis- (6-methyl-.61, -tetrahydrobenzyl) -amine can be prepared starting from free ammonia and 6-methyl-z13-tetrahydrobenzaldehyde, the latter compound being easy to prepare by depositing crotonaldehyde with butadiene. further bis- (1,5-endomethylene-.613-tetrahydrobenzyl) -amine.

(IX) Sekundara diaminer med formeln R2 R,R,' R,' Ra '\CR / R,\ / ,'R, C' \/\ / \ / C—CH,—NH—Z—NH—G112—C R, /\ R4CR7 Rs R, erballas om foreningar med formeln R. R1R1' R2' /\ / R,' CC R71/ C/ \\R4' R,' Rs' 1 B3 C' R, R,' /C\ Fla' C C—CH=N—Z—N=CH—G G (XI) Rs' G R7'/ \r,/ \ p R,' eller fiireningar med formeln R2 R7. its R,\ C\"R,R,',C/ \Ra' \c/ \ / C—CH,--N=Z ---1\I—CH,C/ N / C 1 R8 CCG / \ / \, IA,' / R •c/ 4R, /\/\ R, R6R6' R' (XIII) — — van iR1', R2, R2', R3, R3'y R40 R4') R5, R1, R,', R„ R7', R„ R,', R0 och R,' och Z ha den ovan angivna bestydelsen, eller deras bildningskomponenter underkastas en hydrering, vilken icke Astadkommer flagon mattning av C = Cdubbelbindningarna i cyklohexenringen. (IX) Secondary diamines of the formula R2 R, R, 'R,' Ra '\ CR / R, \ /,' R, C '\ / \ / \ / C — CH, —NH — Z — NH — G112— CR, / \ R4CR7 Rs R, is represented by compounds of the formula R. R1R1 'R2' / \ / R, 'CC R71 / C / \\ R4' R, 'Rs' 1 B3 C 'R, R,' / C \ Fla 'CC — CH = N — Z — N = CH — GG (XI) Rs' G R7 '/ \ r, / \ p R,' or compounds of the formula R2 R7. its R, \ C \ "R, R, ', C / \ Ra' \ c / \ / C — CH, - N = Z --- 1 \ I — CH, C / N / C 1 R8 CCG / \ / \, IA, '/ R • c / 4R, / \ / \ R, R6R6' R '(XIII) - - of iR1', R2, R2 ', R3, R3'y R40 R4') R5, R1 , R 1, R 2, R 7 ', R 4, R 4,', R 0 and R 4 'and Z have the above-mentioned designation, or their formation components are subjected to a hydrogenation which does not cause flake matting of the C = C double bonds in the cyclohexene ring.

De schiffska baserna med formeln (XII) kunna erhalla,s genom kondensation av 2 mol av en aldehyd med formeln (VIII) med 1 mol ay en diprimdr di- eller polyamin, sasom etylendiamin, propylendiamin, hexametylendiamin, dietylentriamin, trietylentetraamin, tetraetylenpentamin, diaminocyklohexan, fenylendiamin, bensidin, p,p'-diaminodifenylmetan och p,p'-diaminodifenylsulfid, -sulfon eller -oxid. The schiff bases of formula (XII) can be obtained by condensation of 2 moles of an aldehyde of formula (VIII) with 1 mole of a diprimderial di- or polyamine, such as ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepycloamine , phenylenediamine, benzidine, p, p'-diaminodiphenylmethane and p, p'-diaminodiphenylsulfide, sulfone or oxide.

De schiffska baserna med formeln (XIII) kunna erhAllas genom kondensation av 2 mol av en amin med formeln (XI) med 1 mol ay en dialdehyd sasom glyoxal, malealdehyd, succinaldehyd, ftalaldehyd och tereftalaldehyd. The schiff bases of formula (XIII) can be obtained by condensation of 2 moles of an amine of formula (XI) with 1 mole of a dialdehyde such as glyoxal, malealdehyde, succinaldehyde, phthalaldehyde and terephthalaldehyde.

Vid anydndning av polyaminer med mer an 2 primara amingrupper, sasom 1,2,3-triaminopropan eller triaminobensen, eller av polyaldehyder med mer an 2 aldehydgrupper erhaller man schiffska baser eller ddrav genom hydrering erhallna aminer med formeln (XI) med mer in tvA vid sekundara aminkvayeatomer bundna cyklohexenrester, dvs. resten Z an i detta fall substituerad med ytterligare rester med formeln R1 R2 \ / RoR3 \/ —NH—CH2—C R8 13„/c/ R6 R Hydreringen enligt uppfinningen av foreningarna med formeln (V), (XII) eller (XIII) kan she enligt vanliga reduktionsforfaranden, vilka Astadkomma en. hydrering air — C N, — C N — 0 eller —C' -grupper utan samtidig hydrering \NH, av C = C-dubbelbindningen i cyklohexenkarnan. Warm forfaranden Aro exempelvis reduktion med natrium i alkoholiska medier och reduktion med litium-aluminiumhydrid. Conversion of polyamines with more than 2 primary amine groups, such as 1,2,3-triaminopropane or triaminobenzene, or of polyaldehydes with more than 2 aldehyde groups gives Schiff bases or hydrocarbons obtained by hydrogenation amines of formula (XI) with more in tvA at secondary amine vapor atoms attached cyclohexene residues, i.e. the residue Z in this case substituted by further residues of the formula R1 R2 / RoR3 \ / —NH — CH2 — C R8 13 „/ c / R6 R The hydrogenation according to the invention of the compounds of formula (V), (XII) or (XIII ) she can according to usual reduction procedures, which Estadkomma en. hydrogenation air - C N, - C N - 0 or -C 'groups without simultaneous hydrogenation \ NH, of the C = C double bond in the cyclohexene nucleus. Warm processes Aro for example reduction with sodium in alcoholic media and reduction with lithium aluminum hydride.

For vissa foreningar, sasom eyklohexennitril, lampar sig aven den katalytiska hydreringen i narvaro av katalysatorer, sasom Raney-nickel eller kopparkromit. For some compounds, such as eyklohexenitrile, catalytic hydrogenation is also present in the presence of catalysts, such as Raney nickel or copper chromite.

Epoxideringen enligt uppfinningen av C = Cdubbelbindningarna i cyklohexenringarna sker enligt vanliga forfaranden, t. ex. med hjdlp av perAttiksyra eller perbensoesyra. The epoxidation according to the invention of the C = C double bonds in the cyclohexene rings takes place according to usual procedures, e.g. with the aid of peracetic acid or perbenzoic acid.

De nya epoxidforeningarna enligt uppfinningen med formeln (I) reagera med vanliga hardningsmedel for epoxidforeningar. De kunna saledes genom tillsats av sadana hdrdare genomhardas eller fOrses med tvarforbindningar analogt med andra polyfunktionella epoxidforeningar eller epcoddhartser. Sasom sadana hdrdare ifrAgakomma basiska eller foretradesvis sura foreningar. Lampliga dro exempelvis aminer eller amider, sasom alifatiska och aromatiska, primara, sekunddra och tertidra aminer, t.ex. mono-, di- och tributylaminer, p-fenylendiamin, etylendiamin, N,N-dietyletylendiamin, dietylentriamin, trietylentetraamin, tetraetylenpentaamin, trimetylamin, dietylamin, trietanolarnin, Mannich-baser, piperidin, piperazin, guanidin och guanidinderivat, shsom fenyldiguanidin, difenylguanidin, dicyandiamid, anilinformaldehydhartser, karbamid-formaldehydhartser, melamin-formaldehyd-hartser, polymerer av aminostyrener, polyamider, t. ex. sadana av alifatiska polyaminer och di- eller trimeriserade, omAttade fettsyror, isocyanat, isotiocyanat; flervarda fenoler, t. ex. resorcinol, hydrokinon, kinon, fenolaldehydhartser, oljemodifierade f enolaldehydhartser, reaktionsprodukter av aluminiumalkoholat eller -fenolat med tautomert reagerande foreningar av typen acetattikester, Friedel-Crafts-katalysatorer, t. ex. AlC12, SbC1„ SnC1,, FeC12, ZnC12, BF, och deras komplex med organiska foreningar; fosforsyra. Man al-wander foretrddesvis hdrdare av flerbasiska karbonsyror och deras anhydrider, t.ex. ftalsyraanhydrid, metylendometylentetrahydroftalsyraanhydrid, dodecenylbdrnstenssyraanhydrid, hexahydroftalsyraanhydrid, hexaklorendometylentetrahydroftalsyraanhydrid och deras blandningar; malein- eller barnstenssyraanhydrid, eyentuellt tillsammans med acceleratorer, sasom tertiara aminer. The novel epoxide compounds of the invention of formula (I) react with conventional curing agents for epoxide compounds. Thus, by the addition of such hardeners, they can be cured or crosslinked analogously to other polyfunctional epoxide compounds or epcode resins. As such adherents come from basic or preferably acidic compounds. For example, amine or amides, such as aliphatic and aromatic, primary, secondary and tertiary amines, e.g. mono-, di- and tributylamines, p-phenylenediamine, ethylenediamine, N, N-diethylethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, trimethylamine, diethylamine, triethanolarnine, Mannich bases, piperidine, piperazine, guanidinidane and guanidinylanidine , aniline formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, polymers of amino styrenes, polyamides, e.g. such as aliphatic polyamines and di- or trimerized, unsaturated fatty acids, isocyanate, isothiocyanate; polyphenols, e.g. resorcinol, hydroquinone, quinone, phenolaldehyde resins, oil-modified phenolaldehyde resins, reaction products of aluminum alcoholate or phenolate with tautomeric reacting compounds of the acetate ester type, Friedel-Crafts catalysts, e.g. AlCl2, SbCl2, SnCl2, FeCl2, ZnCl2, BF, and their complexes with organic compounds; phosphoric acid. Al-wander is preferably preferred hardener of polybasic carboxylic acids and their anhydrides, e.g. phthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, hexachloromethylenetetrahydrophthalic anhydride and their mixtures; maleic or succinic anhydride, optionally together with accelerators, such as tertiary amines.

Uttrycket »hardning» betyder i detta sammanhang ornvandlingen air de ovanndmnda epoxiderade foreningarna till olosliga och osmdltbara hartser. The term "curing" in this context means the conversion of the above-mentioned epoxidized compounds into insoluble and insoluble resins.

De nya epoxidforeningarna eller deras blandningar med hardare kunna fore hdrdningen i vilken fas som heist forsattas med fyllmedel, mjukningsmedel, fdrggivande dmnen etc. Sasom fyllmedel kan man exempelvis anyanda asfalt, bitumen, glasfibrer, glimmer, kvartsmjEd, calmlosa, kaolin, finfordelad kiselsyra (AEROSIL) eller metallpulver. The new epoxide compounds or their mixtures with harder can pre-harden in which phase heist is continued with fillers, plasticizers, forgetting agents, etc. As fillers, for example, any other asphalt, bitumen, glass fibers, mica, quartz smith, calmlosa, kaolin, finely divided silicic acid ( ) or metal powder.

Epoxidforeningarna enligt uppfinningen eller deras blandningar med hardare kunna med eller utan fyllmedel eller i losning eller emulsion anvdndas som textilhjalpmedel, lamineringshartser, lacker, ytbehandlingsmedel, doppningshartser, gjuthartser, pressmassor, bestryknings-, fyll- oak spackelmassor, bindemedel och liknande eller fOr framstdllning av sadana medel. The epoxide compounds according to the invention or their mixtures with hardeners can be used with or without fillers or in solution or emulsion as textile auxiliaries, laminating resins, varnishes, surface treatment agents, dipping resins, casting resins, compacts, coatings, filler fillers, binders and the like. average.

I foljande exempel beteckna delar viktdelar och pro cent viktprocent. Temp eraturerna arc angivna I celsiusgrader. In the following examples, parts denote parts by weight and percent by weight. Temperatures arc specified in degrees Celsius.

Exempel 1. a) Framstallning ay his-(zls-tetra-- bydrobensy1)-arnin. 922 delar Z13-tetrahydrobensonitril hydreras i en med omroringsanordning forsedd autoklav vid 131-132° och 140 atm begynnelsetryek i narvaro av 40 delar kopparkromit. Efter upptagning av 398800 volymdelar irate 6— — (normalbetingelser) avbrytes reduktionen.Katalysatorn franfiltreras och filtratet destilleras. Forutom fordroppar, som innehalla A3-tetrahydrobensylamin, destillera vid 162-164° och 14 mm Hg 580 delar bis-03-tetrahydrobensyl)-amin. n =1,5059. Example 1. a) Preparation of the his- (zls-tetra-- bydrobenzyl) -arnine. 922 parts of Z13-tetrahydrobenzonitrile are hydrogenated in an agitator equipped with a stirrer at 131-132 ° and 140 atm initial pressure in the presence of 40 parts of copper chromite. After uptake of 398800 parts by volume irate 6— - (normal conditions), the reduction is stopped. The catalyst is filtered off and the filtrate is distilled. In addition to pre-droplets containing A3-tetrahydrobenzylamine, distill at 162-164 ° and 14 mm Hg 580 parts of bis-03-tetrahydrobenzylamine. n = 1.5059.

En losning av 229 delar A3-tetrahydrobensylamin i 750 delar bensen forsattes med 227 delar A3-tetrahydrobensaldehyd i 750 volymdelar bensen, varvid uppvarmning och avskiljande av vat-ten genast intrader. Blandningen upphettas till kokning och befrias Iran vatten i en destilleringsanlaggning pa i »Makromolekulare Chemie», 7, (1951), sid. 84-85 beskrivet sat. Losningsmedlet avdunstas och aterstoden destilleras i vakuum vid 11 mm Hg. Vid 147° destillera 382 delar (92 % av den teoretiska mangden) schiffsk bas. 51,0 delar av den ovan beskrivna schiffska basen ltisas i 188 delar absolut alkohol och forsattas Mom loppet av 30 minuter med totalt 23,3 delar natrium i stycken om 3-4 g vardera. Darefter kokas blandningen under aterflOdskylning till fullstanding uppltisning av natriummetallen. Den Ater avkylda massan Mlles i 500 delar isvatten. Den bildade oljan franskiljes, forsattes med 160 volymdelar 2-n svavelsyra och destilleras med vattenanga, tills 2000 delar vatten ha kondenserat. Destillatet fOrkastas. Blandningen installes pa alkalisk reaktion med stark natriumhydroxid och extraheras med eter. Efter torkning Over natriumsulf at indunstas och extratet destilleras vid 11 mm Hg. Vid 152-157° destillera 42,8 delar (84 % av den teoretiska mangden) bis(A3-tetrahydrobensyl)-amin. 54 delar A3-tetrahydrobensaldehyd 18sas i 170 volymdelar metanol och forsattas med 7,7 delar ammoniumklorid i 25 delar vatten och 26 volymdelar 25-procentig ammoniak, varvid blandningen blir varm och en fanning bildas. Man hydrerar sedan i narvaro av 13 delar raneynickel vid 56-65° och 70-120 atmosfarer vate, tills den teoretiska mangden har upptagits. Katalysatorn franfiltreras. Efter utdrivning av losningsmedlet upptages aterstoden i 500 volymdelar eter och skakas tva ganger med 200 volymdelar 2-n svavelsyra varje gang. De sura vattenlosningarna fOrenas, installas pa alkalisk reaktion med koncentrerad natriumhydrcodd och extraheras tya ganger med 250 volymdelar eter. Eterextraktet torkas Over natriumsulfat, indunstas och destilleras vid 14 mm Hg. Vid 60-70° overga. 19 delar A3-tetrahydrobensylamin (35 % av den teoretiska mangden) och vid 141-156° 24 delar bis-(A3- tetrahydrobensyl)-amin (47%). A solution of 229 parts of A3-tetrahydrobenzylamine in 750 parts of benzene was continued with 227 parts of A3-tetrahydrobenzaldehyde in 750 parts by volume of benzene, heating and separation of the water immediately entering. The mixture is heated to boiling and liberated from Iranian water in a distillation plant in Macromolecular Chemistry, 7, (1951), p. 84-85 described sat. The solvent is evaporated and the residue is distilled in vacuo at 11 mm Hg. At 147 ° distill 382 parts (92% of theory) of Schiff's base. 51.0 parts of the above-described schiff base are dissolved in 188 parts of absolute alcohol and the Mom is continued for 30 minutes with a total of 23.3 parts of sodium in pieces of 3-4 g each. The mixture is then boiled under reflux until complete thawing of the sodium metal. The Ater cooled mass Mlles in 500 parts of ice water. The oil formed is separated, continued with 160 parts by volume of 2-n sulfuric acid and distilled with water vapor, until 2000 parts of water have condensed. The distillate is discarded. The mixture is installed on alkaline reaction with strong sodium hydroxide and extracted with ether. After drying Over sodium sulfate to evaporate and the extract is distilled at 11 mm Hg. At 152-157 ° distill 42.8 parts (84% of theory) of bis (A3-tetrahydrobenzyl) -amine. 54 parts of A3-tetrahydrobenzaldehyde are added to 170 parts by volume of methanol and continued with 7.7 parts of ammonium chloride in 25 parts of water and 26 parts by volume of 25% ammonia, whereby the mixture becomes hot and a formation is formed. It is then hydrogenated in the presence of 13 parts of raney nickel at 56-65 ° and 70-120 atmospheres of vate, until the theoretical amount has been taken up. The catalyst is filtered off. After evaporation of the solvent, the residue is taken up in 500 parts by volume of ether and shaken twice with 200 parts by volume of 2-n sulfuric acid each time. The acidic aqueous solutions are reconstituted, installed on alkaline reaction with concentrated sodium hydride and extracted ten times with 250 parts by volume of ether. The ether extract is dried over sodium sulfate, evaporated and distilled at 14 mm Hg. At 60-70 ° surrender. 19 parts of A3-tetrahydrobenzylamine (35% of theory) and at 141-156 ° 24 parts of bis- (A3-tetrahydrobenzyl) -amine (47%).

N,N-bis-(tetrahydrobensyl)-formamid. 102 delar bis-(43-tetrahydrobensyl)-amin kokas i en med natriumsulfat beskickad destillationsapparat med 300 volymdelar bensen och 55 delar 85-procentig myrsyra, tills destillatet ãr klart. Losningsmedlet och overskottet av myrsyra avdunstas i vattenstralvakuum och aterstoden destilleras vid 0,2 mm Hg. Man erhaller 106 delar (91 % av den teoretiska mangden) N,N-bis-(43-tetra hydrobensyl)-formamid med kokpunkten 141°. n 2o = 1,5218. N, N-bis- (tetrahydrobenzyl) -formamide. 102 parts of bis- (43-tetrahydrobenzyl) -amine are boiled in a distillation apparatus equipped with sodium sulfate with 300 parts by volume of benzene and 55 parts of 85% formic acid, until the distillate is ready. The solvent and excess formic acid are evaporated in a water jet vacuum and the residue is distilled at 0.2 mm Hg. 106 parts (91% of theory) of N, N-bis- (43-tetrahydrobenzyl) -formamide having a boiling point of 141 ° are obtained. n 2o = 1.5218.

* Analys: CH230N beralinat: C 77,20 % H 9,94 % funnet: C 77,10 % H 9,94 % N,N-bis-(3,4-epoxihexahydrobensyl)-formamid. 93 delar bis-(z13-tetrahydrobensy1)-formamid losas i 400 volymdelar bensen. Efter tillsats av 20 delar vattenfritt natriumacetat tillsattas droppvis inorn 31 minuter 180 delar 42-procentig perattiksyra. Genom yttre kylning halles ternperaturen vid 29°. Efter ytterligare 30 minuter vid 29° har 94 % av den. teoretiska mangden perattiksyra forbrukats. Den undre vattenfasen franskiljes och bensenen tvattas tre ganger med 200 delar vatten varje gang, vidare med 200 delar 2-n soda och med 50 delar mononatriumfosfatlosfling. Vattenfaserna extraheras tva ganger med 300 delar bensen varje gang. De forenade extrakten torkas Over natriumsulf at och indunstas sedan. Efter torkning i hogvakuum vid 60-70' erhallas 89 delar epoxid. Produkten kristalliserar da den far std nagon tid. * Analysis: CH 230N beralinate: C 77.20% H 9.94% Found: C 77.10% H 9.94% N, N-bis- (3,4-epoxyhexahydrobenzyl) -formamide. 93 parts of bis- (z13-tetrahydrobenzyl) -formamide are dissolved in 400 parts by volume of benzene. After the addition of 20 parts of anhydrous sodium acetate, 180 parts of 42% of peracetic acid are added dropwise within 31 minutes. By external cooling, the temperature is kept at 29 °. After another 30 minutes at 29 °, 94% of it. theoretical amount of peracetic acid consumed. The lower aqueous phase is separated and the benzene is washed three times with 200 parts of water each time, further with 200 parts of 2-soda and with 50 parts of monosodium phosphate release. The aqueous phases are extracted twice with 300 parts of benzene each time. The combined extracts are dried over sodium sulfate and then evaporated. After drying in a high vacuum at 60-70 ', 89 parts of epoxide are obtained. The product crystallizes when it is left on for some time.

Epoxidhalt: 6,8 ekvivalenter/kg (90 % av den teoretiska mangden). 45,0 delar N,N-bis-(3,4-epoxihexahydrobensyl)- formamid blandas vid 80° med 50,5 delar metylendometylen-tetrahydroftalsyraanhydrid. Blandningen halles i en gjutform av aluminium. Efter cirka 2 timmar vid 110° intrader stelning (Gelierung). Gjutkroppen hardas 15 timmar vid 110°, 23 timmar vid 150° och 13 timmar vid 200°. Den uppvisar foljande mekaniska egenskaper: slaghojhallfasthet 8,53 cmkg/cm3 formbestandighet enligt Martens: 149°. Epoxide content: 6.8 equivalents / kg (90% of theory). 45.0 parts of N, N-bis- (3,4-epoxyhexahydrobenzyl) formamide are mixed at 80 ° with 50.5 parts of methylendomethylene tetrahydrophthalic anhydride. The mixture is poured into an aluminum mold. After about 2 hours at 110 °, solidification (gelation) enters. The casting body is cured for 15 hours at 110 °, 23 hours at 150 ° and 13 hours at 200 °. It has the following mechanical properties: impact strength 8,53 cmkg / cm3 dimensional stability according to Martens: 149 °.

Exempel 2. N,N-bis-(43-tetrahydrobensy1)-acetamid. 102,5 delar bis-03-tetrahydrobensy1yamin forsattas droppvis under °mitring med 75 delar attiksyraanhydrid. Blandningen blir varm och dess temperatur stiger till 150°. Efter 30 minuter vid 140° avdestilleras den bildade attiksyran och tiverskottet av attiksyraanhydrid i vattenstralvakuum. Aterstoden ger vid destillation 117,9 delar (95 % av den teoretiska mangden) bis-(A3- tetrahydrobensyl)-acetamid med kokpunkten 131 —136° vid 0,05 mm Hg. Example 2. N, N-bis- (43-tetrahydrobenzyl) -acetamide. 102.5 parts of bis-03-tetrahydrobenzylamine are added dropwise during metering with 75 parts of attic anhydride. The mixture becomes hot and its temperature rises to 150 °. After 30 minutes at 140 °, the attic acid formed and the tiver shot of attic anhydride are distilled off in a water jet vacuum. On distillation, the residue gives 117.9 parts (95% of theory) of bis- (A3-tetrahydrobenzyl) -acetamide, boiling point 131-136 ° at 0.05 mm Hg.

Analys: C161-10N beraknat: 77,68 % H 10,19 % funnet: 77,56 % H 10,19 %. Analysis: C161-10N Calculated: 77.68% H 10.19% Found: 77.56% H 10.19%.

N,N-bis-(3,4-epoxihexahydrobensyl)-acetamid 102 delar bis-(213-tetrahydrobensyl)-amin Nandas med 400 delar volymdelar bensen. Darefter tillsatter man under omrtiring och kylning med is inorn 14 minuter 51 delar attiksyraanhydrid. Temperaturen stiger till 25°. Efter tillsats av 30 delar vattenfritt natriumacetat tillsattas inorn 40 minuter under omroring portionsvis 230 delar 42-procentig perattiksyra. Genom kylning med is Mlles temp eraturen vid 29°. Darefter avbryter man kylningen och later komponenterna reagera - -7 ytterligare 38 minuter vid 29°. Darefter liar 90 % av den teoretiska mangden perattiksyra forbrukats. Vattenskiktet franskiljes och bensenen tvattas tre ganger med 500 volymdelar vatten varje gang, 400 volymdelar 2-n soda och 50 volymdelar mononatriumfosfat. De vattenhaltiga delarna extraheras med 500 volymdelar bensen. Extrakten giva vid indunstning tillsammans 95 delar av ett tjockflytande harts, som innehaller 6,33 epoxidekvivalenter per kg (89 % av den teoretiska mangden). N, N-bis- (3,4-epoxyhexahydrobenzyl) -acetamide 102 parts of bis- (213-tetrahydrobenzyl) -amine Nandas with 400 parts by volume of benzene. Then, during stirring and cooling with ice for 14 minutes, 51 parts of acetic anhydride are added. The temperature rises to 25 °. After the addition of 30 parts of anhydrous sodium acetate, 230 parts of 42% of 42% peracetic acid are added portionwise within 40 minutes with stirring. By cooling with ice Mlles temperature at 29 °. Then the cooling is stopped and the components are allowed to react - -7 another 38 minutes at 29 °. Thereafter, 90% of the theoretical amount of peracetic acid is consumed. The aqueous layer is separated and the benzene is washed three times with 500 parts by volume of water each time, 400 parts by volume of 2-soda and 50 parts by volume of monosodium phosphate. The aqueous parts are extracted with 500 parts by volume of benzene. When extracted, the extracts together yield 95 parts of a viscous resin containing 6.33 epoxide equivalents per kg (89% of theory).

Hardningsforsok. 39 delar smalt ftalsyraanhydrid blandas vid cirka 110° med 47,5 delar N,N-bis-(3,4-epoxihexahydrobensyl)-acetamid. Blandningen Mlles i en gjutform av aluminium och hardas 45 timmar vid 150°. Gjutkroppen visar ftiljande fysikaliska egenskaper: b Oj hallfasthet:6,03 kg/cm, slagbojhallfasthet:5,84 cmkg/cm, vartnebestandighet enligt Martens (DIN):190°. Hardening test. 39 parts of narrow phthalic anhydride are mixed at about 110 ° with 47.5 parts of N, N-bis- (3,4-epoxyhexahydrobenzyl) -acetamide. The mixture is poured into an aluminum mold and cured for 45 hours at 150 °. The casting body shows the following physical properties: b Oj half strength: 6.03 kg / cm, impact buoy strength: 5.84 cm kg / cm, heat resistance according to Martens (DIN): 190 °.

Exempel 3. N,N-bis-(43-tetrahydrobensy1)-ptoluensulfonamid. Example 3. N, N-bis- (43-tetrahydrobenzyl) -ptoluenesulfonamide.

En blandning av 205 delar bis-(&-tetrahydrobensyl)-amin i 300 volymdelar etylenklorid och 500 volymdelar 2-n natriumhydroxid forsattes droppvis under god omroring med en losning av 191 delar p-toluen-sulfonsyraklorid i 500 volymdelar etylenklorid. Genom kylning med is Mlles temperaturen vid 0. Efter 2 timmar vid rumstemperatur franskiljes vattenskiktet och extraheras tva ganger med 100 volymdelar 0,5-n natriumhydroxid varje gang, torkas Over natriumsulfat och indunstas i vakuum. Man erhaller 358,2 delar (99,7 % av den teoretiska mangden) N,N-bis(zi2- tetrahydrobensyl) -p -toluensulfonamid med smaltpunkten 87-89,°. A mixture of 205 parts of bis - (& - tetrahydrobenzyl) -amine in 300 parts by volume of ethylene chloride and 500 parts by volume of 2-n sodium hydroxide was added dropwise with good stirring with a solution of 191 parts of p-toluenesulfonic acid chloride in 500 parts by volume of ethylene chloride. By cooling with ice Mlles the temperature at 0. After 2 hours at room temperature, the aqueous layer is separated and extracted twice with 100 parts by volume of 0.5-n sodium hydroxide each time, dried over sodium sulfate and evaporated in vacuo. 358.2 parts (99.7% of theory) of N, N-bis (zi2-tetrahydrobenzyl) -p-toluenesulfonamide, m.p. 87-89 °, are obtained.

Efter kristallisering tre ganger ur metanol erhailer man ett preparat med smaltpunkten 95- 96°. After crystallization three times from methanol, a preparation with a melting point of 95-96 ° is obtained.

Analys: C2,14,„0,NS beraknat: C 70,16 %H 8,13 % S 8,92 % funnet:C 70,14 %H 8,% S 8,84 % N,N-bis-(3,4-epoxihexahydrobensyl)-p-toluensulfonamid. 358 delar av p-toluensulfonamiden losas 11500 volymdelar etylenklorid och forsattas med 50 delar vattenfritt natriumacetat. mom 45 minuter tillsattas droppvis under omroring och kylning med is vid 30° 450 delar 42-procentig perattiksyra. Blandningen Mlles ytterligare 75 minuter vid ° genom lamplig kylning. Darefter har 97 % av den teoretiska mangden perattiksyra filrbrukats. Losningen tvattas tre ganger med 500 volymdelar vatten varje gang och tva ganger med 200 volymdelar 2-n soda varje gang, torkas Over natriumsulfat och indunstas sedan. Man erhaller 375 delar kristalliserad epoxid. Produkten visar en epoxidhalt av 4,72 epoxidekvivalenter per kg (= 92,3 % av den teoretiska mangden). Analysis: C 2.14, 0.20 NS calcd: C 70.16% H 8.13% S 8.92% Found: C 70.14% H 8% S 8.84% N, N-bis- ( 3,4-epoxyhexahydrobenzyl) -p-toluenesulfonamide. 358 parts of the p-toluenesulfonamide are dissolved in 11500 parts by volume of ethylene chloride and continued with 50 parts of anhydrous sodium acetate. 45 minutes is added dropwise while stirring and cooling with ice at 30 ° 450 parts of 42% peracetic acid. Mix the mixture for another 75 minutes at 0 ° C by gentle cooling. Thereafter, 97% of the theoretical amount of peracetic acid has been filtered. The solution is washed three times with 500 parts by volume of water each time and twice with 200 parts by volume of 2-soda each time, dried over sodium sulfate and then evaporated. 375 parts of crystallized epoxide are obtained. The product shows an epoxide content of 4.72 epoxide equivalents per kg (= 92.3% of the theoretical amount).

For analys kristalliseras ett preparat tre ganger ur metanol. Smaltpunkt 131-132°. C 2,1-1,90 ,NS beraknat: C 64,42 % H 7,46 % 0 16,% funnet:C 64,67 % H 7,66 % 0 16,02 % Gj utkroppar. 56 delar smalt epoxid blandas vid cirka 130' med 32 delar ftalsyraanhydrid och fyllas i en gjutform av aluminium. Efter 43 minuter yid. 150° stelnar blandningen. Gjutkroppen hardas 45 minuter vid 150°. Den visar fOljande formbestandighet enligt Martens (DIN): 138°. For analysis, a preparation is crystallized three times from methanol. Melting point 131-132 °. C 2.1-1.90, NS calculated: C 64.42% H 7.46% 0 16,% Found: C 64.67% H 7.66% 0 16.02% Gj bodies. 56 parts of narrow epoxide are mixed at about 130 'with 32 parts of phthalic anhydride and filled into an aluminum mold. After 43 minutes yid. 150 ° solidifies the mixture. The casting body hardens for 45 minutes at 150 °. It shows the following dimensional stability according to Martens (DIN): 138 °.

Exempel 4. N,N-bis-(4 8- Le trahydrob ensyl)-uretan. 102,5 delar bis-(A3-tetrahydrobensyl)-amin 10- sas i 400 volymdelar etylenklorid och fOrsattas med 250 volymdelar 2-n soda. Under god omroring och kylning tillsattas 56 delar klormyrsyraetylester droppvis Mom 30 minuter vid 5-7°. Daref ter later man blandningen antaga rumstemperatur under omroring. Etylenkloriden skiljes och vattenskiktet, som uppvisar ett pHvarde av 6 extraheras med 250 volymdelar etylenklorid. Extrakten forenas, torkas Over natriumsulfat och indunstas. Aterstoden ger vid destillation 119,5 delar (86 % av den teoretiska mangden) N,N-bis-(zl'-tetrahydrobensyl)-uretan med kokpunkten 131-136° (0,02 mm Hg); n =- 1,5006. Example 4. N, N-bis- (4-8-Le trahydrobensyl) -urethane. 102.5 parts of bis- (A3-tetrahydrobenzyl) -amine 10 are added in 400 parts by volume of ethylene chloride and are replaced by 250 parts by volume of 2-n soda. With good stirring and cooling, 56 parts of chloroformic acid ethyl ester are added dropwise with Mom 30 minutes at 5-7 °. The mixture is then allowed to warm to room temperature with stirring. The ethylene chloride is separated and the aqueous layer, which has a pH value of 6, is extracted with 250 parts by volume of ethylene chloride. The extracts are combined, dried over sodium sulfate and evaporated. On distillation, the residue gives 119.5 parts (86% of theory) of N, N-bis- (z1'-tetrahydrobenzyl) -urethane, boiling point 131-136 ° (0.02 mm Hg); n = - 1.5006.

Analys: C „H „ 0 ,N beraknat: C 73,60 % H 9,81 % N 5,0% funnet:C 73,6% H 9,7 % N 5,2 % N,N-bis-(3,4-epoxihexahydrobensyl)-uretan. 108 delar N,N-bis-(43-tetrahydrobensyl)-uretan ltisas i 500 volymdelar bensen on forsattas med 20 delar natriumacetat. Darefter tillsatter man droppvis under kylning och omroring Mom 30 minuter vid 30° 200 delar 42-procentig perattiksyra och hailer temperaturen vid 30° i ytterligare 2 timmar. Darefter har 97 % av den teoretiska mangden perattiksyra forbrukats. Analysis: C 7 H 11 N 2 N: C 73.60% H 9.81% N 5.0% Found: C 73.6% H 9.7% N 5.2% N, N-bis- ( 3,4-epoxyhexahydrobenzyl) -urethane. 108 parts of N, N-bis- (43-tetrahydrobenzyl) -urethane are dissolved in 500 parts by volume of benzene and added with 20 parts of sodium acetate. It is then added dropwise during cooling and stirring for 30 minutes at 30 ° to 200 parts of 42% peracetic acid and the temperature is maintained at 30 ° for a further 2 hours. Thereafter, 97% of the theoretical amount of peracetic acid has been consumed.

Bensenlosningen tvattas tre ganger med 150' delar isvatten varje gang och tva ganger med 150 volymdelar utspadd sodalosning varje gang. De vattenhaltiga delarna extraheras med 250 volymdelar bensen. De forenade extrakten torkas Over natriumsulfat och indunstas. Man erhaller vattenklart harts med en epmddhalt av 5,67 ekvivalenter/kg (87,7 % av den teoretiska mangden). The benzene solution is washed three times with 150 parts of ice water each time and twice with 150 parts by volume of diluted soda solution each time. The aqueous parts are extracted with 250 parts by volume of benzene. The combined extracts are dried over sodium sulfate and evaporated. Water-clear resin with an average content of 5.67 equivalents / kg (87.7% of theory) is obtained.

Exempel 5. N, N-bis-(zl3-tetrahydrobensyl)-cyanamid. 102,5 delar bis-(4'-tetrahydrobensyl)-amin losas i 400 volymdelar etylenklorid och overskiktas med 250 volymdelar 2-n sodalosning. Under god omroring och kylning tillsatter man droppvis vid -2 till + 2' Mom 15 minuter 54 delar bromcyan, losta i 200 volymdelar etylenklorid. Darefter later man blandningen antaga rumstemperatur under standig omroring. Vattenskiktet visar nu ett pHvarde av 6. 8- - Etylenkloriden franskiljes och vattnet extraheras med 200 volymdelar etylenklorid. Extrakten fOrenas, torkas Over natriumsulfat, indunstas och destilleras. Vid 141 148° och 0,04 mm Hg Overga 97,3 delar (85 % av den teoretiska mang- den)N,N-bis-03-tetrahydrobensyl)-cyanamid. n 2o15157. Example 5. N, N-bis- (z13-tetrahydrobenzyl) -cyanamide. 102.5 parts of bis- (4'-tetrahydrobenzyl) -amine are dissolved in 400 parts by volume of ethylene chloride and overlaid with 250 parts by volume of 2-n soda solution. With good stirring and cooling, 54 parts of bromocyanate are added dropwise at -2 to + 2 '. Mom 15 minutes, dissolve in 200 parts by volume of ethylene chloride. The mixture is then allowed to warm to room temperature with constant stirring. The aqueous layer now shows a pH value of 6. 8- - The ethylene chloride is separated and the water is extracted with 200 parts by volume of ethylene chloride. The extracts are combined, dried over sodium sulfate, evaporated and distilled. At 141 148 ° and 0.04 mm Hg Overga 97.3 parts (85% of theory) N, N-bis-03-tetrahydrobenzyl) -cyanamide. n 2o15157.

Analys: C,,H 2,N, beraknat: C 78,21 % H 9,63 % N 12,16 % funnet:C 78,07 % H 9,83 % N 11,91 % N,N-bis-(A3-epoxihexahydrobensyl)-cyanamid. 85,0 delar bis-(A3-tetrahydrobensyl)-cyanamid losas i 300 volymdelar bensen. Efter tillsats av 20 delar natriumacetat -Mir man portionsvis 190 delar 42-procentig perattiksyra under kylning och omriir vid 0 och inorn 33 minuter. Efter ytterligare 60 minuter vid 30-28° har 96 % av den teoretiska mangden perattiksyra forbrukats. Bensenen tvattas tre ganger med 100 volymdelar vatten varje gang och tva ganger med 100 volymdelar sodalOsning varje gang. Vattenfaserna extraheras med 250 volymdelar bensen. De forenade extrakten giva vid indunstning 77,0 delar (80 % av den teoretiska mangden) av ett vattenklart harts med en epoxidhalt av 6,76 ekvivalenter/kg (88,6 % av den teoretiska mangden). Analysis: C 11 H 21 N 2 Calcd: C 78.21% H 9.63% N 12.16% Found: C 78.07% H 9.83% N 11.91% N, N-bis- (A3-epoxyhexahydrobenzyl) -cyanamide. 85.0 parts of bis- (A3-tetrahydrobenzyl) -cyanamide are dissolved in 300 parts by volume of benzene. After the addition of 20 parts of sodium acetate, 190 parts of 42% of peracetic acid are added portionwise under cooling and stirred at 0 and within 33 minutes. After a further 60 minutes at 30-28 °, 96% of the theoretical amount of peracetic acid has been consumed. The benzene is washed three times with 100 parts by volume of water each time and twice with 100 parts by volume of soda solution each time. The aqueous phases are extracted with 250 parts by volume of benzene. The combined extracts give on evaporation 77.0 parts (80% of theory) of an aqueous clear resin having an epoxide content of 6,76 equivalents / kg (88.6% of theory).

Exempel 6. Di-schiffsk has av LP-tetrahydrobensaldehyd och etylendiamin. 31 delar etylendiamin i 200 volymdelar bensen blandas med 118 delar 93-procentigda-tetrahydrobensaldehyd. Ur blandningen avskiljes omedelhart vatten. Den upphettas till kokning och befrias frau vatten i en destillationsapparat. Usningen indunstas och aterstoden destilleras i hogvakuum. Vid 117-126° on 0,01 mm Hg erhallas 107 delar (88 % av den teoretiska mangden) dischiffsk bas. n = 1,5177. Example 6. Diffuse resin of LP-tetrahydrobenzaldehyde and ethylenediamine. 31 parts of ethylenediamine in 200 parts by volume of benzene are mixed with 118 parts of 93% tetrahydrobenzaldehyde. Immediately separate hard water from the mixture. It is heated to boiling and freed from water in a distillation apparatus. The ushing is evaporated and the residue is distilled in a high vacuum. At 117-126 ° on 0.01 mm Hg, 107 parts (88% of theory) of the dischiff base are obtained. n = 1.5177.

Analys: C1e1124N2 beraknat: C 78,63 %H 9,90 % N 11,46 % funnet:C 78,84 %H 10,19 % N 11,14 % N,N'-bis-(13-tetrahydrobensy1)-ety1endiamin. 122 delar av den ovan beskrivna di-schiffska basen lams i 800 delar absolut alkohol och fOrdttas portionsvis med totalt 92 delar natrium, Varvid blandningen borjar koka. Mot slutet av reaktionen tillsattas ytterligare 100 delar alkohol och kokas tills natriummetallen ar fullstandigt lost. Efter avsvalning tillsattas 1750 delar vatten, den bilclade oljan franskiljes och vattenfasen extraheras tva ganger med 250 volymdelar bensen. Extraktet fbrenas med oljan, torkas Over natriumsulfat och indunstas. Vid destillation av Aterstoden i hogvakuum (0,05-0,08 mm Hg) erlianas 102 delar (82 % av den teoretiska mangden) N,N'-bis-03-tetrahydrobensylyetylendiamin med kokpunkten 132-142°. n = 1,5092. Analysis: C 1112 124 N 2 Calculated: C 78.63% H 9.90% N 11.46% Found: C 78.84% H 10.19% N 11.14% N, N'-bis- (13-tetrahydrobenzyl) - ethylenediamine. 122 parts of the above-described di-schiff base are paralyzed in 800 parts of absolute alcohol and are added portionwise with a total of 92 parts of sodium, the mixture starting to boil. Towards the end of the reaction, another 100 parts of alcohol are added and boiled until the sodium metal is completely dissolved. After cooling, 1750 parts of water are added, the carclad oil is separated and the aqueous phase is extracted twice with 250 parts by volume of benzene. The extract is combined with the oil, dried over sodium sulfate and evaporated. When distilling the Aterstoden in a high vacuum (0.05-0.08 mm Hg), 102 parts (82% of theory) of N, N'-bis-03-tetrahydrobenzylethylenediamine with a boiling point of 132-142 ° are obtained. n = 1.5092.

Analys: _ beraknat: C 77,36 % H 11,36 % N 11,28 % funnet: C 77,46 % H 11,26 % N 11,40 % N,NI-diacety1-N,N'-bis-(43-tetrahydrobensy1)- etylendiamin. 99 delar N,N1-bis-(ii-tetrahydrobensyl)-etylendiamin blandas under kylning med 90 delar attiksyraanhydrid. Efter utdrivning av den bildade attiksyran i vattenstralvakuum destilleras Aterstoden i hogvakuum. Vid cirka 200° (0,07 mm Hg) overga 102 delar av en mycket viskos vatska, som kristalliserar langsamt, cla den lamnas att sta. en langre tid. Analysis: Calculated: C 77.36% H 11.36% N 11.28% Found: C 77.46% H 11.26% N 11.40% N, NI-diacetyl-N, N'-bis- (43-tetrahydrobenzyl) -ethylenediamine. 99 parts of N, N1-bis- (ii-tetrahydrobenzyl) -ethylenediamine are mixed under cooling with 90 parts of acetic anhydride. After expulsion of the attic acid formed in a water jet vacuum, the residue is distilled in a high vacuum. At about 200 ° (0.07 mm Hg), 102 parts of a highly viscous liquid, which crystallizes slowly, leaves it to stand. a longer time.

Analys: C201-132N 2 beraknat: N 8,43 % funnet: N 8,53 c/o N,N'-diacetyl-N,N'-bis-(3,4-ep oxihexahydrobensyl)-etylendiamin. 33 delar av den ovannamnda produkten losas i 200 volymdelar bensen. Vid cirka 20° tillsattas droppvis 840 volymdelar av en losning av perktiksyra i bensen, som innehaller 19 delar perattiksyra. Blandningen uppvarmes langsamt till 27° och tvattas efter 7 timmar tva ganger med 200 volymdelar iskall 1-n soda varje gang och sedan med 200 volymdelar mattad koksaltlOsning. Efter torkning Over natriumsulfat avdunstas losningsmedlet. Analysis: C201-132N2 Calculated: N 8.43% Found: N 8.53 c / o N, N'-diacetyl-N, N'-bis- (3,4-epoxyhexahydrobenzyl) -ethylenediamine. 33 parts of the above product are dissolved in 200 parts by volume of benzene. At about 20 °, 840 parts by volume of a solution of peractic acid in benzene containing 19 parts of peracetic acid are added dropwise. The mixture is slowly heated to 27 ° and washed after 7 hours twice with 200 parts by volume of ice-cold 1-soda each time and then with 200 parts by volume of matted brine. After drying Evaporate the solvent over sodium sulphate.

Det erhallna epoxidhartset (25 delar) kan omkristalliseras ur koltetraklorid under kylning. Smaltpunkt 128-129°. The resulting epoxy resin (25 parts) can be recrystallized from carbon tetrachloride under cooling. Melting point 128-129 °.

Det kan hardas till en gjutkropp pa fOljande salt: 2,33 delar epoxidharts, 1,26 delar ftalsyraanhydrid och 0,05 delar bisido-tetrahydrobensyl)- metyl-amin smaltas, blandas val och hallas i en gjutform. Efter 15 minuter vid 150° har massan stelnat och hardat fullstandigt efter ytterligare 30 minuter. It can be cured to a casting body on the following salt: 2.33 parts of epoxy resin, 1.26 parts of phthalic anhydride and 0.05 parts of bisido-tetrahydrobenzyl) -methylamine are melted, mixed selectively and poured into a mold. After 15 minutes at 150 °, the mass has solidified and hardened completely after another 30 minutes.

Den som hardningsaccelerator anvanda bis(43-tetrahydrobensyl)-metyl-aminen kan erhallas pa foljande aft: 51 delar bis-(Z13-tetrahydrobensyl)-amin losas under kylning med is i 32 delar 90-procentig myrsyra. Blandningen uppvarmes med 24 delar 36,6-procentig formaldehyd och upp\Tames till 50°, varvid en stark gasutveckling app-trader under 20 minuter. Darefter Mlles lOsningen vid 1000 ytterligare 14 timmar. Efter tillsats av 200 volymdelar 2-n saltsyra destilleras med vattenanga, tills 2000 delar ha gatt Over. Blandningen installes pa alkalisk reaktion med 100 volymdelar koncentrerad natriumhydroxid och extraheras tre ganger med 500 delar eter varje gang. Nar eterlosningen har torkats Over vattenfritt kaliumkarbonat, bortdrives losningsmedlet och aterstoden destilleras vid 11 mm Hg. Vid 147 -159° destillera 46 delar bis-(43-tetrahydrobensyl)-metyl-amin.Analys av destillatet ger fOljande forbranningsvarden: C „H 2,N beraknat: C 82,13 % H 11,49 % N 6,38 % funnet:C 82,21 % H 11,59 % N 6,53 % Exempel 7. di-schiffsk has av Z13-tetrahydrobensaldehyd och hexametylendiamin. 58 delar hexametylendiamin i 200 volymdelar bensen blandas med 118 delar 93-procentig Z13-• - 9 tetrahydrobensaldehyd. Det franskilda vattnet avlagsnas genom destillation. Efter avdrivning av losningsmedlet destilleras aterstoden vid 1541590 (0,05 mm Hg). Utbyte: 144 delar (96 % av den teoretiska mangden), n g = 1,5074. The bis (43-tetrahydrobenzyl) -methylamine used as hardening accelerator can be obtained as follows: 51 parts of bis- (Z13-tetrahydrobenzyl) -amine are dissolved under ice-cooling in 32 parts of 90% formic acid. The mixture is heated with 24 parts of 36.6% formaldehyde and heated to 50 °, with a strong gas evolution app-trader for 20 minutes. Then Mlles the solution at 1000 for another 14 hours. After adding 200 parts by volume, 2-n hydrochloric acid is distilled with water vapor, until 2000 parts have reached Over. The mixture is installed on alkaline reaction with 100 parts by volume of concentrated sodium hydroxide and extracted three times with 500 parts of ether each time. Once the ether solution has been dried over anhydrous potassium carbonate, the solvent is driven off and the residue is distilled at 11 mm Hg. At 147 DEG-159 DEG, distill 46 parts of bis- (43-tetrahydrobenzyl) methylamine. Analysis of the distillate gives the following calorific value: C, H2, N calculated: C 82.13% H 11.49% N 6.38% Found: C 82.21% H 11.59% N 6.53% Example 7. Diffuse resin of Z13-tetrahydrobenzaldehyde and hexamethylenediamine. 58 parts of hexamethylenediamine in 200 parts by volume of benzene are mixed with 118 parts of 93% of Z13-9-9 tetrahydrobenzaldehyde. The separated water is removed by distillation. After evaporation of the solvent, the residue is distilled at 1541590 (0.05 mm Hg). Yield: 144 parts (96% of theory), n g = 1.5074.

Analys: C20H3 2N 2 beraknat: C 79,94 % H 10,74 % N 9,32 °,70 funnet:C 79,55 % H 10,82 % N 9,48 % N,N'-bis-(A3-tetrahydrobensy1)-hexamety1endiamin. 525 delar av den oven beskrivna schiffska basen blandas med 3800 volymdelar absolut alkohol. Sedan tillsatter man langsamt under omroring 325 g metalliskt natrium i form av stycken om cirka 4 g, varvid blandningens temperatur stiger till kokpunkten. Mot slutet av reaktionen kokar man under dterflodskylning, tills natriummetallen fir fullstdndigt upplost. Efter avsvalning tillsattas 4000 delar vatten, den bildade oljan franskiljes och vattenfasen extraheras tva ganger med 500 volymdelar bensen vane gang. Extraktet forenas med oljan och befrias fran vatten genom destillation. Bensenen avdunstas och den erhallna Aterstoden destilleras, varvid 440 delar N,r-bis(43-tetrahydrobensyl)-hexametylendiamin erhallas yid 150-160° (0,05 mm Hg). n g -= 1,5032. Analysis: C20H3 2N2 calcd: C 79.94% H 10.74% N 9.32 °, 70 Found: C 79.55% H 10.82% N 9.48% N, N'-bis- (A3 -tetrahydrobenzyl) -hexamethylenediamine. 525 parts of the schiff base described above are mixed with 3800 parts by volume of absolute alcohol. Then 325 g of metallic sodium in the form of pieces of about 4 g are slowly added with stirring, the temperature of the mixture rising to the boiling point. Towards the end of the reaction, boil under reflux until the sodium metal is completely dissolved. After cooling, 4000 parts of water are added, the oil formed is separated and the aqueous phase is extracted twice with 500 parts by volume of benzene as usual. The extract is combined with the oil and freed from water by distillation. The benzene is evaporated and the resulting residue is distilled to give 440 parts of N, r-bis (43-tetrahydrobenzyl) -hexamethylenediamine at 150-160 ° (0.05 mm Hg). n g - = 1.5032.

Analys: C113 6N2 beraknat: C 78,88 % H 11,92 % N 9,20 % funnet: C 78,55 % H 11,90 % N 9,27 % N, N'-diacetyl-N,N'-bis-(3,4-epoxihexahydrob ensyl)-hexametylendiamin. 430 delar N,N'-bis-(tetrahydrobensyl-hexametylendiamin losas i 2000 volymdelar bensen, 289 delar attiksyraanhydrid tillsattas droppvis, varvid temperaturen, genom kylning med is, Mlles vid 15-38°. Darefter tillsatter man 60 delar vattenfritt natriumacetat och tillsatter under 42 minuter portionsvis 600 delar 42-procentig perattiksyra. Temperaturen Mlles yid 30° genom kylning. Efter ytterligare 2 timmar vid 32° tvattas bensenen tre ganger med 500 volymdelar vatten vane gang, tre ganger med 500 volymdelar 2-n sodalosning varje gang och slutligen med 50 volymdelar 1-m mononatriumfosfatlosning. Vattenfasen extraheras med 750 volymdelar bensen. Extrakten fOrenas, torkas Over natriumsulfat och indunstas. Man erhaller 478 delar produkt, som innehaller 4,26 epoxidekvivalenter per kg (89,5 % av den teoretiska mangden). • Framstallning av en gjutkropp. 46,6 delar epoxid blandas yid 95° med 30,2, delar metyl-endometylen-tetrahydroftalsyraanhydrid och halls i en gjutform av aluminium. Blandningen stelnar efter 155 minuter vid 150°. Efter 40 timmars hardning yid 150° visar gjutkroppen foljande mekaniska egenskaper: bojhallfasthet vid 50°: 11,39 kg/mm2 slagbbjhallfasthet:12,27 cmkg/cm2. Analysis: C113 6N2 Calculated: C 78.88% H 11.92% N 9.20% Found: C 78.55% H 11.90% N 9.27% N, N'-diacetyl-N, N'- bis- (3,4-epoxyhexahydrobenzyl) -hexamethylenediamine. 430 parts of N, N'-bis- (tetrahydrobenzyl-hexamethylenediamine are dissolved in 2000 parts by volume of benzene, 289 parts of acetic anhydride are added dropwise, the temperature, by cooling with ice, Mlles at 15-38 °. Then 60 parts of anhydrous sodium acetate are added and added below. 42 minutes portionwise 600 parts 42% peracetic acid The temperature Mlles yid 30 ° by cooling After a further 2 hours at 32 ° the benzene is washed three times with 500 parts by volume of water as usual, three times with 500 parts by volume of 2-n soda solution each time and finally with 50 parts by volume of 1-m monosodium phosphate solution The aqueous phase is extracted with 750 parts by volume of benzene The extracts are combined, dried over sodium sulphate and evaporated to give 478 parts of product containing 4.26 epoxide equivalents per kg (89.5% of theory). 46.6 parts of epoxide are mixed at 95 ° with 30.2 parts of methyl endomethylene tetrahydrophthalic anhydride and poured into an aluminum mold. solidifies after 155 minutes at 150 °. After 40 hours of curing at 150 °, the casting body shows the following mechanical properties: buoyancy at 50 °: 11.39 kg / mm2 impact strength: 12.27 cmkg / cm2.

Exempel 8. N,N'-bis448-tetrahydrobensyI). hexametylen-di-uretan. 61 delar N,N'-bis-(43-tetrahydrobensyl)-hexametylendiamin losas i 200 volymdelar etylen-_ klorid och tiverskiktas med 250 volymdelar 2-n. sodalosning. Under god omroring Yid 0-10° tillsattas 50 delar klormyrsyraetylester droppvis, varvid en Mining bildas. Da man efter avslutadt tillsats av klormyrsyraestern har omrort ytter-1 ligare 1 timme, tillsatter man 1000 volymdelar. etylacetat och franskiljer vattenskiktet. Losningent tvattas med 100 delar 2-n soda och 100 delar, mattad koksaltlosning, torkas Over natriumsulfat .och indunstas. Ur aterstoden utvinner man genom destillation vid cirka 200° (0,04 mm Hg) 66 delar, N,N'-bis- (iP-tetrahydrobensyl) -hexametylen- diuretan. Example 8. N, N'-bis448-tetrahydrobenzyl). hexamethylene-di-urethane. 61 parts of N, N'-bis- (43-tetrahydrobenzyl) -hexamethylenediamine are dissolved in 200 parts by volume of ethylene chloride and trisolated with 250 parts by volume of 2-n. soda solution. With good stirring Yid 0-10 °, 50 parts of chloroformic acid ethyl ester are added dropwise, forming a Mining. After the addition of the chloroformic acid ester has been stirred for a further 1 hour, 1000 parts by volume are added. ethyl acetate and separates the aqueous layer. The solution is washed with 100 parts of 2-soda and 100 parts, matted brine, dried over sodium sulfate and evaporated. From the residue, 66 parts of N, N'-bis- (1β-tetrahydrobenzyl) -hexamethylenediurethane are recovered by distillation at about 200 ° (0.04 mm Hg).

Analys: C26H4404N2 beraknat: C 69,60 % H 9,89 % N 6,24 % funnet:C 69,1% H9,8 % N 6,% N,N'-bis-(3,4-epoxihexahydrobensyl)-hexametylen-diuretan. 57,5 delar N,N' -his- -tetrahydrobensyly hexametylen-diuretan losas i 300 volymdelar bensen. Man tillsatter 60 delar 42-procentig pen: attiksyra under omroring och kylning i narvaro av 5 delar natriumacetat och inom 13 minuter och later reaktionen fortga ytterligare 1 timme vid 30°. Darefter har 81 % av den teoretiska mangden perattiksyra ftirbrukats. Den organiska fasen; tvattas tre ganger med 100 volymdelar isvattea och tva ganger med 100 delar utspadd sodalosning. Vattenfasen extraheras med 250 delar bensen. De forenade extrakten giva efter torkning och indunstning 54,2 delar diepoxid med en epoxidhalt av 3,85 epoxidekvivalenter per kg. Analysis: C 26 H 44 O 4 N 2 Calculated: C 69.60% H 9.89% N 6.24% Found: C 69.1% H9.8% N 6,% N, N'-bis- (3,4-epoxyhexahydrobenzyl) - hexamethylene-diurethane. 57.5 parts of N, N '-his- -tetrahydrobenzyl hexamethylene diurethane are dissolved in 300 parts by volume of benzene. 60 parts of 42% penic acid are added with stirring and cooling in the presence of 5 parts of sodium acetate and within 13 minutes and the reaction is allowed to proceed for a further 1 hour at 30 °. Thereafter, 81% of the theoretical amount of peracetic acid has been consumed. The organic phase; washed three times with 100 parts by volume of ice water and twice with 100 parts of diluted soda solution. The aqueous phase is extracted with 250 parts of benzene. The combined extracts give, after drying and evaporation, 54.2 parts of diepoxide with an epoxide content of 3.85 epoxide equivalents per kg.

Exempel 9. Di-schiffsk has av A2-tetrahydrobensaldehyd och fenylendiamin. 108 delar p-fenylendiamin i 500 volymdelar bensen blandas med 238 delar 93-pro centig tetrahydrobe,nsaldehyd och befrias frail vatten i en destillationsapparat. Bensenen avdestilleras sedan och aterstoden destilleras vid 0,03 mm Hg och cirka 200°. Utbyte: 241 delar (82 % av den teoretiska mangden). Produkten stelnar vid avkylning. Example 9. Diffuse resin of 22-tetrahydrobenzaldehyde and phenylenediamine. 108 parts of p-phenylenediamine in 500 parts by volume of benzene are mixed with 238 parts of 93% tetrahydrobe, nsaldehyde and liberated from free water in a distillation apparatus. The benzene is then distilled off and the residue is distilled at 0.03 mm Hg and about 200 °. Yield: 241 parts (82% of theory). The product solidifies on cooling.

N,IV-bis-(43-tetrahydrobensyl)-p-fenylendiamin. - 73 delar av den ovan beskrivna di-schiffska basen losas i 500 volymdelar absolut alkohol. I losningen infOras langsamt 46 delar natrium. Sedan tillsattas ytterligare 200 volymdelar absolut alkohol och kokas, tills natriummetallen dr fullstandigt uppltist. Under reaktionen franskiljes produkten i form av sma droppar. Efter avsvalning tillsattas 500 volymdelar bensen och 2000 delar vatten. Vattenskiktet franskiljes. Den organiska fasen indunstas och aterstoden destilleras yid 0,05 mm Hg och cirka 200°, varvid 56 delar N,Nr-bis-(A3-tetrahydrobensyl)- p -fenylen- diamin omedelbart kristallisera. Produkten ken kristalliseras ur cyklohexan. Smaltpunkt 96°. N, IV-bis- (43-tetrahydrobenzyl) -p-phenylenediamine. 73 parts of the above-described di-schiff base are dissolved in 500 parts by volume of absolute alcohol. 46 parts of sodium are slowly introduced into the solution. Then add another 200 parts by volume of absolute alcohol and boil until the sodium metal is completely dissolved. During the reaction, the product is separated in the form of droplets. After cooling, 500 parts by volume of benzene and 2000 parts of water are added. The water layer is separated. The organic phase is evaporated and the residue is distilled at 0.05 mm Hg and about 200 °, whereby 56 parts of N, N-bis- (A3-tetrahydrobenzyl) -p-phenylenediamine immediately crystallize. The product is crystallized from cyclohexane. Melting point 96 °.

— — Analys: C201128N2 beraknat: C 81,03 %H 9,52 funnet:C 81,19 %H 9,62 % % N 9,45 N 9,27 % % N,N1-diacetyl-N,Y-bis-(3,4-epoxihexahydrobensyl)-p-fenylendiamin. ' 50,3 delar N,N1-bis-(tetrahydrobensyl)p-fenylendiamin losas i 300 volymdelar bensen. Sedan inforas 35,0 delar attiksyraanhydrid och blandningen kokas 15 minuter. Man avkyler till 30°, tillsatter 10 delar natriumacetat och epoxiderar 40 minuter vid 30-° med 75 delar 42-procentig perattiksyra. Produkten vidarebehandlas pa i foregaende exempel beskrivet satt. Man erhailer 63,4 delar kristalliserad produkt med en epoxidhalt av 3,36 ekvivalenter per kg. Analysis: C201128N2 Calculated: C 81.03% H 9.52 Found: C 81.19% H 9.62%% N 9.45 N 9.27%% N, N1-diacetyl-N, Y-bis - (3,4-epoxyhexahydrobenzyl) -p-phenylenediamine. 50.3 parts of N, N1-bis- (tetrahydrobenzyl) p-phenylenediamine are dissolved in 300 parts by volume of benzene. Then 35.0 parts of acetic anhydride are introduced and the mixture is boiled for 15 minutes. Cool to 30 °, add 10 parts of sodium acetate and epoxidize for 40 minutes at 30 ° with 75 parts of 42% peracetic acid. The product is further processed in the manner described in the previous example. 63.4 parts of crystallized product with an epoxide content of 3.36 equivalents per kg are obtained.

Exempel 10. N,N-bis-(A2-tetrahydrobensyl)- stearamid. Example 10. N, N-bis- (A2-tetrahydrobenzyl) stearamide.

Till en blandning av 102,5 delar tetrahydrobensyl)-amin i 400 volymdelar etylenklorid och 53 delar vattenfri soda, losta i 400 volymdelar vatten, sattas droppvis 152 delar stearinsyraklorid under god omroring vid 7-13° och mom 27 minuter Man (mirk ytterligare tre timmar vid rumstemperatur. Vattenfasen visar ett pH-varde av 7. Den undre fasea (etylenklorid) franskiljes, tvattas tva ganger med 200 volymdelar 2-n salpetersyra varje gang och med 100 volymdelar 2-n kaliumbikarbonatlosning, torkas Over natriumsulfat och indunstas. Produkten (236 delar, 100 % av den teoretiska mangden) kristalliserar delvis. To a mixture of 102.5 parts of tetrahydrobenzyl) -amine in 400 parts by volume of ethylene chloride and 53 parts of anhydrous soda, dissolved in 400 parts by volume of water, 152 parts of stearic acid chloride are added dropwise with good stirring at 7-13 ° and for 27 minutes. The aqueous phase shows a pH of 7. The lower phase (ethylene chloride) is separated, washed twice with 200 parts by volume of 2-n nitric acid each time and with 100 parts by volume of 2-n potassium bicarbonate solution, dried over sodium sulphate and evaporated. 236 parts, 100% of the theoretical amount) partially crystallizes.

* Ytan starkt angripen. * Surface strongly attacked.

Exempel 12. 6-mety1-113-tetrahydrobensylamin. 278 delar 6-metyl-43-tetrahydrobensaldoxim losas i 3000 volymdelar absolut alkohol. Under omroring tillsattas 320 delar natrium portionsvis, varvid blandningen borjar koka. Man utspader under reaktionen med 1500 volymdelar alkohol. Nar hela mangden natrium har tillforts, kokar man tills metallen har losts fullstandig,t. 3300 delar vatten tillsattas Man extraherar blandningen med 3 x 1000 volymdelar bensen. Bensenlosningarna forenas och indunstas. Aterstoden surgores med 1000 volymdelar 2-n saltsyra under kylning med is och extraheras med 3 x 400 volymdelar eter. Vattenfasen forsattes under kylning med is med 250 delar 50-procentig natriumhydroxidlOsning och extraheras tre ganger med cirka 400 volymdelar bensen. Bensenlosningen torkas Over vattenfritt natriumsulfat, filtreras -och indunstas. Atersto den destilleras 1 vakuum N,N-bis-(3,4-epoxi-hexahydrobensyl)-stearamid 100 delar N,N-bis-(A3-tetrahydrobensy1)-stearamid losas 1500 volymdelar bensen. Man tillsatter vidare under omrtiring 11 delar vattenfritt natriumacetat och portionsvis inom 10 minuter vid 30° 110 delar 42-procentig pera'ttiksyra. Efter ytterligare 85 minuter vid 28-33° franskiljes vattenskiktet. Bensenfasen tvattas med vatten och 2-n soda, tills syroma ha avlagsnats fullstandigt. Losningen torkas over natriumsulfat och indunstas. Man erhaller 103 delar kristalliserad produkt med en halt av 3,25 epoxidekvivalenter per kg. Example 12. 6-Methyl-133-tetrahydrobenzylamine. 278 parts of 6-methyl-43-tetrahydrobenzaldoxime are dissolved in 3000 parts by volume of absolute alcohol. While stirring, 320 parts of sodium are added portionwise, the mixture starting to boil. During the reaction, 1500 parts by volume of alcohol are diluted. When the entire amount of sodium has been added, boil until the metal has completely dissolved. 3300 parts of water are added The mixture is extracted with 3 x 1000 parts by volume of benzene. The benzene discharges are combined and evaporated. The residue is acidified with 1000 parts by volume of 2-n hydrochloric acid while cooling with ice and extracted with 3 x 400 parts by volume of ether. The aqueous phase was continued under ice-cooling with 250 parts of 50% sodium hydroxide solution and extracted three times with about 400 parts by volume of benzene. The benzene solution is dried over anhydrous sodium sulfate, filtered and evaporated. The residue is distilled in vacuo N, N-bis- (3,4-epoxy-hexahydrobenzyl) -stearamide 100 parts of N, N-bis- (A3-tetrahydrobenzyl) -stearamide are dissolved 1500 parts by volume of benzene. Further, 11 parts of anhydrous sodium acetate are added during the stirring, and 110 parts of 42% of peracetic acid are added portionwise within 10 minutes at 30 °. After a further 85 minutes at 28-33 °, the water layer separates. The benzene phase is washed with water and 2-soda, until the acids have been completely removed. The solution is dried over sodium sulphate and evaporated. 103 parts of crystallized product are obtained with a content of 3.25 epoxide equivalents per kg.

Exempel 11. Losningsmedelsbestandighet. Example 11. Solvent resistance.

I 20 delar bis-(3,4-epoxi-hexahydrobensyl)- acetamid losas vid cirka 100° 0,50 delar bortrifluorid-etylamin-komplex. Blandningen fylles i gjutformar av tenn (4 x 1 x 1 cm) och upphettas vid 150°. Efter 60 minuter intruder stelning. Darefter hardas ytterligare 40 thnmar vid 150°. In 20 parts of bis- (3,4-epoxy-hexahydrobenzyl) -acetamide is dissolved at about 100 ° 0.50 parts of boron trifluoride-ethylamine complex. The mixture is filled into tin molds (4 x 1 x 1 cm) and heated at 150 °. After 60 minutes, solidification occurs. Then harden another 40 thmmar at 150 °.

Pa samma sun framstalles gjutkroppar av 6,6'-dimety1-3,4-epoxi- hexahydrobensy1-3',4'-epoxi-hexahydrobensoat. Blandningen stelnar efter 6 minuter. On the same sun, castings are prepared from 6,6'-dimethyl-3,4-epoxy-hexahydrobenzyl-3 ', 4'-epoxy-hexahydrobenzoate. The mixture solidifies after 6 minutes.

De erhallna gjutkropparna inlaggas i losningsmedel. De enligt B erhallna gjutkropparna borja snarl att svalla (viktokning) o chsonderfalla (Wetter (viktminskning), under det att de enligt A framstallda gjutkropparan aro oforandrade och icke visa nagra ytskador. Foljande tabell visar gjutkroppamas viktokning respektive -minskning. The resulting castings are loaded into solvent. The castings obtained according to B begin to swell (weight gain) and decay (Wetter (weight loss)), while the castings produced according to A are unchanged and do not show any surface damage.The following table shows the weight gain and reduction of the castings respectively.

Vikt after 32 min 83 min 2 3/4 tim 18 tim 3353 3353 3353 3 3949* 3904 3676 7 3630603 3896 4 4968 3366* genom en Vigreuxkolonn. Produkten kokar vid 72-74° vid 15 mm Hg. Weight after 32 min 83 min 2 3/4 hr 18 hr 3353 3353 3353 3 3949 * 3904 3676 7 3630603 3896 4 4968 3366 * through a Vigreux column. The product boils at 72-74 ° at 15 mm Hg.

Analys: Vid titrering i metanol med 1-n saltsyra till onnslag for bromfenolbla'tt forbrukas 7,97 syraekvivalenter/kg (teoretisk mangd: 7,97 ekvivalenter/kg). Analysis: When titrated in methanol with 1-n hydrochloric acid to escape bromophenol blue, 7.97 acid equivalents / kg are consumed (theoretical amount: 7.97 equivalents / kg).

C81-1,N beraknat: N 11,19 % funnet: N 11,38 % Schiffs has av 6-metyl-A3-tetrahydrobensaldehyd och 6-mety1-A3-tetrahydrobensylamin. C81-1, N calculated: N 11.19% Found: N 11.38% Schiffs has 6-methyl-A3-tetrahydrobenzaldehyde and 6-methyl-A3-tetrahydrobenzylamine.

En kokande blandning av 100 delar 6-metylA2-tetrahydrobensa1dehyd och 250 volymdelar bensen forsattes droppvis med 100 delar 6-metylAu-tetrahydrobensylamin. Pet bildade vattnet (13 delar) franskiljes i en vattenavskilj are. Losningen indunstas och aterstoden destilleras i vakuum. Kokpunkt cirka 110° vid 0,7 ram Hg. A boiling mixture of 100 parts of 6-methylA2-tetrahydrobenzaldehyde and 250 parts by volume of benzene was added dropwise with 100 parts of 6-methylAu-tetrahydrobenzylamine. The pet formed water (13 parts) is separated in a water separator. The solution is evaporated and the residue is distilled in vacuo. Boiling point about 110 ° at 0.7 ram Hg.

Gjutkropp enligt A A Liisningsmedel Kloroform Aceton Dimetylformamid Ursprunglig vikt mg 3353 3881 36 3879 4968 3290 - t80 083 -11 Analys: C „H,,N beraknat: N 6,05 % funnet: N 6,10 % Bis(6-mety1-L13-tetrahydrobensy1)-amin. 159 delar av den schiffska basen blandas med 400 delar absolut alkohol. 65 delar natrium inforas i form av stycken om 5-g i losningen, sa att fri metall hela tiden finns narvarande. Under reaktionen utspades blandningen med 150 delar absolut alkohol. Nar hela mangden natrium har inforts, kokas tills metallen har lost sig. Darefter tillsattas 500 delar isvatten. Efter avsvalning extraherar man med tre portioner om vardera cirka. 300 volymdelar bensen. De fOrenade bensenlosningarna torkas Over vattenfritt natriumsulfat, filtreras och indunstas. Aterstoden destilleras i vakuum. Kokpunkt 119-121° vid 0,8 mm Hg. Cast body according to AA Leaching agent Chloroform Acetone Dimethylformamide Original weight mg 3353 3881 36 3879 4968 3290 - t80 083 -11 Analysis: C „H ,, N calculated: N 6.05% Found: N 6.10% Bis (6-methyl-L13 -tetrahydrobenzyl) -amine. 159 parts of the Schiff base are mixed with 400 parts of absolute alcohol. 65 parts of sodium are introduced in the form of 5-g pieces in the solution, so that free metal is always present. During the reaction, the mixture was diluted with 150 parts of absolute alcohol. When the entire amount of sodium has been imported, boil until the metal has dissolved. Then 500 parts of ice water are added. After cooling, extract with three portions of approx. 300 parts by volume of benzene. The combined benzene solutions are dried over anhydrous sodium sulfate, filtered and evaporated. The residue is distilled in vacuo. Boiling point 119-121 ° at 0.8 mm Hg.

Analys: Yid titrering av basen i metanol med 1-n saltsyra och bromfenolblatt som indikator forbrukas 4,28 syraekvivalenter/kg (teoretisk mangd: 4,28 ekvivalenter/kg). Analysis: Yid titration of the base in methanol with 1-n hydrochloric acid and bromophenol leaf as indicator consumes 4.28 acid equivalents / kg (theoretical amount: 4.28 equivalents / kg).

C„H"Nberaknat: N 6,00 % funnet: N 6,17 % N,N-bis(6-metyl-i13-tetrahydrobensyl)-acetamid. C "H" Nberaknat: N 6.00% Found: N 6.17% N, N-bis (6-methyl-13-tetrahydrobenzyl) -acetamide.

En losning av 46,6 delar bis(6-mety1-i13-tetrahydrobensyl)-amin i 200 volymdelar bensen fOrsattes droppvis med 30 delar attiksyraanhydrid Darefter kokas blandningen en timme under Aterflodskylning. Darefter tillsattas 20 delar metanol och blandningen indunstas i vattensugyakuum. Atersto den destilleras i hogvakuum. Kokpunkt cirka 144° vid 0,18 mm Hg. A solution of 46.6 parts of bis (6-methyl-13-tetrahydrobenzyl) -amine in 200 parts by volume of benzene was added dropwise with 30 parts of acetic anhydride. The mixture was then boiled for one hour under re-flooding. Then 20 parts of methanol are added and the mixture is evaporated in a water suction vacuum. Atersto it is distilled in a high vacuum. Boiling point about 144 ° at 0.18 mm Hg.

Analys: C„H2ONberaknat: N 5,09 % funnet: N 5,00 % N,N-bis(3,4-epoxi-6-metyl-hexahydrobensyl)- acetamid. 42 delar N,N-bis(6-metyl-L13-tetrahydrobensyl)- acetamid losas i 136 delar etylacetat. Man till-salter 2 delar vattenfritt natriumacetat och Mom 45 minuter under omroring 70 delar cirka 40- procentig perattiksyra (vidare innehallande cirka 46 % attiksyra, 3 % vdteperoxid, 10 % vatten och 1 % svavelsyra). Temperaturen Mlles vid vid 40° genom kylning. Efter ytterligare 1 1/2 timmes vid 40° har den teoretiska mangden perattiksyra forbrukats. Blandningen utspades med 150 volymdelar etylbensen och tvattas tva ganger med 200 delar vatten varje gang. Losningen indunstas i vattensugvakuum under thlsats av etylbensen. Aterstoden, ett klart, ljust harts, befrias fran de sista resterna losningsmedelvid 1000 I hogvakuum. Produkten innehaller 5,66 epoxidekvivalenter/kg. [Titrerad enligt det av A. J. Durbetaki beskrivna forfarandet, Anal. Chem. 28, 2000 (1956)]. Analysis: C 2 H 2 ON Calculated: N 5.09% Found: N 5.00% N, N-bis (3,4-epoxy-6-methyl-hexahydrobenzyl) -acetamide. 42 parts of N, N-bis (6-methyl-L13-tetrahydrobenzyl) -acetamide are dissolved in 136 parts of ethyl acetate. Add 2 parts of anhydrous sodium acetate and Mom 45 minutes with stirring 70 parts of about 40% peracetic acid (further containing about 46% acetic acid, 3% hydrogen peroxide, 10% water and 1% sulfuric acid). The temperature is measured at 40 ° by cooling. After a further 1 1/2 hours at 40 °, the theoretical amount of peracetic acid has been consumed. The mixture was diluted with 150 parts by volume of ethylbenzene and washed twice with 200 parts of water each time. The solution is evaporated in a water suction vacuum while adding ethylbenzene. The residue, a clear, light resin, is freed from the last residual solvent at 1000 L in high vacuum. The product contains 5.66 epoxide equivalents / kg. [Titrated according to the procedure described by A. J. Durbetaki, Anal. Chem. 28, 2000 (1956)].

Exempel 13. 2,5-mety1en-z13-tetrahydrobensy1amin. Example 13. 2,5-Methylene-z13-tetrahydrobenzylamine.

Av cyklopentadien och akrylnitril bereder man pa ka.nt satt en blandning av endo- och exo-2,5- metylen-43-tetrahydrobensonitril. 200 delar av denna nitril blandas med 3300 volymdelar absolut alkohol. 320 delar natrium i stycken om cirka g infiiras portionsvis. Under reaktionen utspades med 1800 volymdelar absolut alkohol. Nar hela mangden natrium har inforts, kokas tills metallen har lOst sig fullstandigt. Darefter tillsattas 3300 delay vatten. Blandningen extraheras efter avkylning tre ganger med 1000 volymdelar bensen varje gang. De forenade bensenlosningarna indunstas. Aterstoden surgores under kylning med is med 1000 volymdelar 2-n saltsyra och extraheras Ire ganger med 400 volymdelar eter varje gang. Vattenfaserna installas pa alkalisk reaktion med 250 delar 50-procentig natriumhydroxidlOsning under kylning med is och extraheras med 300 volymdelar bensen. Bensenextrakten fbrenas, tor- kas Over vattenfritt natriumsulfat, filtreras och indunstas. Aterstoden destilleras. Kokpunkt 6871° vid 16 mm Hg. A mixture of endo- and exo-2,5-methylene-43-tetrahydrobenzonitrile may be prepared from cyclopentadiene and acrylonitrile. 200 parts of this nitrile are mixed with 3300 parts by volume of absolute alcohol. 320 parts of sodium in pieces of about g are introduced in portions. During the reaction, 1800 parts by volume of absolute alcohol were diluted. When the entire amount of sodium has been imported, boil until the metal has completely dissolved. Then 3300 delay water is added. The mixture is extracted after cooling three times with 1000 parts by volume of benzene each time. The combined benzene solutions are evaporated. The residue is acidified under ice-cooling with 1000 parts by volume of 2-n hydrochloric acid and extracted once with 400 parts by volume of ether each time. The aqueous phases are installed on alkaline reaction with 250 parts of 50% sodium hydroxide solution under cooling with ice and extracted with 300 parts by volume of benzene. The benzene extracts are combined, dried over anhydrous sodium sulfate, filtered and evaporated. The residue is distilled. Boiling point 6871 ° at 16 mm Hg.

Analys: Produkten innehaller 8,03 basekvivalenter/kg (teoretisk mangd: 8,12 ekvivalenter/kg). Analysis: The product contains 8.03 base equivalents / kg (theoretical amount: 8.12 equivalents / kg).

C8H13Nberaknat: N 11,37 % funnet: N 11,39 % Schiffsk has av 2,5-endometylen-A3-tetrahydrobensaldehyd och 2,5-metylen-L13-tetrahydrobensylamin. C8H13N Calculated: N 11.37% Found: N 11.39% Schiffsk has 2,5-endomethylene-A3-tetrahydrobenzaldehyde and 2,5-methylene-L13-tetrahydrobenzylamine.

En kokande blandning av 100 delar 2,5-endometylen-A3-tetrahydrobensa1dehyd och 250 volymdelar bensen forsattes droppvis med 92,3 delar 2,5-mety1en-.43-tetrahydrobensylamin. Det bildade vattnet franskiljes i en vattenavskiljare. Losningen indunstas och aterstoden destilleras. Kokpunkt 164-167° vid 15 mm Hg. Destillatet kristalliserar delvis. A boiling mixture of 100 parts of 2,5-endomethylene-33-tetrahydrobenzaldehyde and 250 parts by volume of benzene was added dropwise with 92.3 parts of 2,5-methylene-.43-tetrahydrobenzylamine. The water formed is separated in a water separator. The solution is evaporated and the residue is distilled. Boiling point 164-167 ° at 15 mm Hg. The distillate partially crystallizes.

Bis-(2,5-metylen-A3-tetrahydrobensyl)-amin. 113,5 delar av den ovannamnda schiffska basen blandas med 400 delar absolut alkohol. Man infOr 46 delar natrium portionsvis, utspader med 50 delar alkohol och kokar slutligen, tills metallen har lOst sig fullstandigt. Darefter tillsattas 500 delar vatten. Efter avkylning extraheras blandningen Ire ganger med 400 volymdelar bensen varje gang. Bensenlosningarna forenas och indunstas. Aterstoden destilleras i vakuum. Kokpunkt 117-122° vid 0,9 mm Hg. Bis- (2,5-methylene-33-tetrahydrobenzyl) -amine. 113.5 parts of the abovementioned Schiff's base are mixed with 400 parts of absolute alcohol. 46 parts of sodium are introduced in portions, diluted with 50 parts of alcohol and finally boiled until the metal has completely dissolved. Then 500 parts of water are added. After cooling, the mixture is extracted once with 400 parts by volume of benzene each time. The benzene discharges are combined and evaporated. The residue is distilled in vacuo. Boiling point 117-122 ° at 0.9 mm Hg.

Analys: Produkten innehaller 4,32 basekvivalenter/kg. (Teoretisk mangd: 4,36 ekvivalenter/ kg.) C16H23Nberdknat: N 6,11 % funnet: N 5,99 % N, N-bis(2,5-metylen-z13-tetrahydrob ensyl)-acetamid. 45,8 delay bis(2,5-metylen-A3-tetrahydrobensyl)-amin losas i 200 volymdelar bensen och forsattas langsamt med 30 delar attiksyraanhydrid. Darefter kokas losningen cirka 1 timme. Man tillsatter 20 delar metanol och indunstar i vattensugvakuum. Aterstoden destilleras i hogvakuum. Kokpunkt cirka 150° vid 0,08 mm Hg. Analysis: The product contains 4.32 base equivalents / kg. (Theoretical amount: 4.36 equivalents / kg.) C 16 H 23 N Calculate: N 6.11% Found: N 5.99% N, N-bis (2,5-methylene-z13-tetrahydrobensyl) -acetamide. 45.8 delay bis (2,5-methylene-A3-tetrahydrobenzyl) -amine is dissolved in 200 parts by volume of benzene and slowly added with 30 parts of acetic anhydride. The solution is then boiled for about 1 hour. 20 parts of methanol are added and evaporated in a water suction vacuum. The residue is distilled in a high vacuum. Boiling point about 150 ° at 0.08 mm Hg.

Analys:• Ci81-10Nberaknat: N 5,16 % funnet: N 5,17 % 12— — N,N-bis(3,4-epoxi-2,5-metylen-hexahydrobensyl)- acetamid. 41,4 delar N,N-bis(2,5-metylen-.13-tetrahydrobensyl)-acetamid losas i 200 delar etylacetat och forsattas med 3 delar vattenfritt natriumacetat. 55 delar cirka 40-procentig perattiksyra tillsattas droppvis och blandningen Mlles vid 30° under omroring, tills 95 % av den teoretiska mangden perattiksyra ha forbrukats. Blandningen utspades med etylbensen, tvattas tva ganger med 200 delar vatten varje gang och indunstas i vattensugvakuum. Atersto den, ett viskost harts, befrias Iran de sista resterna losningsmedel vid 2 mm Hg och 120'. Epoxidhalten kan icke bestammas med bromvate. 5 delar av produkten blandas vid 115° med 2,5 delar ftalsyraanhydrid. Blandningen over& till en gel efter 5 1/2 timmar vid 120°. Efter 14 timmars hardning vid 120° bildas en hard, oloslig gj utkropp. Analysis: • C 188-10 N Calculated: N 5.16% Found: N 5.17% 12 - - N, N-bis (3,4-epoxy-2,5-methylene-hexahydrobenzyl) -acetamide. 41.4 parts of N, N-bis (2,5-methylene-.13-tetrahydrobenzyl) -acetamide are dissolved in 200 parts of ethyl acetate and continued with 3 parts of anhydrous sodium acetate. 55 parts of about 40% of peracetic acid are added dropwise and the mixture is mixed at 30 ° with stirring until 95% of the theoretical amount of peratic acid has been consumed. The mixture was diluted with ethylbenzene, washed twice with 200 parts of water each time and evaporated in a water suction vacuum. Atersto den, a viscous resin, Iran is released the last residual solvent at 2 mm Hg and 120 '. The epoxide content cannot be determined with bromine cotton. 5 parts of the product are mixed at 115 ° with 2.5 parts of phthalic anhydride. The mixture over & into a gel after 5 1/2 hours at 120 °. After 14 hours of curing at 120 °, a hard, inseparable body is formed.

Claims (8)

Patentansprik:Patent claim: 1. Forfarande for framstallning av nya, sasom textilhjalpmedel, lamineringshartser, lacker, gjuthartser, pressmassor, spackelmassor eller bindemedel larnpliga, kvavehaltiga epoxidforeningar, kannetecknat darav, att fereningar med den all-manna formeln R2R, \ / R, /C \ /R9XI C—C1-12—N- 1,R8 R.,' \ —CH2—C n-1 Rs' R,' 2. / R3' G - \ CC R/ \c/ \R4' 3. \ . R6 ' R6' van i1111, R2, R2r, R3, R3', R4, 114', R6, 115', R„ 11,1, 11„ 117', 118, 118, 118, R9' beteckna lagre alkylrester med 1-1 kolatomer eller vateatomer, varvid R, ochrespektive R,' och R,' tillsam- mans aven kunna beteekna en metylengrupp, X och Y beteckna acyl-, karbalkoxi-, karbaminyl-, cyan- eller sulfonylrester, Z betecknar en R alkylen- R 2, \ /X 118R, \ \/ I C—CH —N- / 0R8 eller fenylenrest, m betecknar ett belt tal med ett varde av hogst 2 och n betecknar ett litet, belt tal, epoxideras genom omsattning med epoxiderande medel, sasom perattiksyra eller perbensoesyra, under bildning av foreningar med den allmanna formeln 4. / R,' /C, \ \ R2' '\, CH2—C R8'0 1/ N CC c/ \114' R,R, /\/\ Rg Rg van RD R11, R2, R2', R3, R31, R4, R4',R,', B.„ B R„R„ Rs', R„ R,', X, V. Z, och n ha den ovan angivna betydelsen. RG R6'1. Process for the preparation of new, such as textile aids, laminating resins, lacquers, casting resins, compacts, putties or binders, nitrogen-containing epoxide compounds, characterized in that compounds of the general formula R2R, \ / R, / C \ / R —C1-12 — N- 1, R8 R., '\ —CH2 — C n-1 Rs' R,' 2. / R3 'G - \ CC R / \ c / \ R4' 3. \. R6 'R6' of 1111, R2, R2r, R3, R3 ', R4, 114', R6, 115 ', R' 11,1, 11 '117', 118, 118, 118, R9 'denote lower alkyl radicals with 1 -1 carbon atoms or hydrogen atoms, wherein R 1 and R 2 and R 2, respectively, together may also represent a methylene group, X and Y represent acyl, carbalkoxy, carbaminyl, cyano or sulfonyl radicals, Z represents an R R 2, \ / X 118R, \ \ / IC — CH —N- / OR8 or phenylene residue, m denotes a belt number with a value of log 2 and n denotes a small, belt number, epoxidized by reaction with epoxidizing agents, such as peracetic acid or perbenzoic acid, to give compounds of general formula 4. / R, '/ C, \ \ R2' '\, CH2 — C R8'0 1 / N CC c / \ 114' R, R, / \ / Rg Rg of RD R11, R2, R2 ', R3, R31, R4, R4', R, ', B. „BR„ R „Rs', R„ R,', X, V. Z, and n ha the meaning given above. RG R6 ' 2. FOrfarande enligt patentanspraket 1, kannetecknat darav, aft foreningar med den allmanna formeln R2 R,R, R2 \ /\ / ,, R R,\ /C\R, /C\ , /R, \ G C—CH2—N—CH2—C c/ I / 118 x R8\ CCCC R: \\c// \R,11/ \c/ \ R4 /\/ \. RG R6R, 1 — —13 van i R1, R,, R3, 114, R„ R,, R„ R„ R, och X ha den i patentanspraket 1 angivna betydelsen, epoxideras genom omsattning med epoxiderande medel.2. A process according to claim 1, characterized in that compounds of the general formula R 2 R 2, R 2, R 2, R 2, R 3, R 2, R 3, R 2, R 3 CH2 — C c / I / 118 x R8 \ CCCC R: \\ c // \ R, 11 / \ c / \ R4 / \ / \. Rg R6R, 1 - 13 van in R1, R ,, R3, 114, R „R ,, R„ R „R, and X having the meaning given in patent claim 1, are epoxidized by reaction with epoxidizing agents. 3. Forfarande enligt patentansprdket 1 eller 2, kannetecknat dãrav, att foreningar med den all-manna formeln CH, \CH, / \ HG CH—CH,—N—CH,—CH CH HC HC—R X R'—CH CH \ CH,/ van i X har den i patentanspraket 1 angivna betydelsen och R och R' beteckna en vdteatom eller en lagmolekylar alkylrest, epoxideras genom omsdttning med epoxiderande medel.3. A process according to claim 1 or 2, characterized in that compounds of the general formula CH, \ CH, / \ HG CH-CH, -N-CH, -CH CH HC HC-RX R'-CH CH \ CH 2 / van in X has the meaning given in claim 1 and R and R 'represent a hydrogen atom or a low molecular weight alkyl residue, epoxidized by reaction with epoxidizing agents. 4. Forfarande enligt nagot ax patentanspraken 1-3, kannetecknat darav, att foreningen med formlen CHCH, / 2\/ \ CH CH—CH,—N—CH,—CH CH IIIIIII CH CH, C=0 CH, CH H\'CH( epoxideras genom omsattning med epoxiderande medel.4. A process according to any one of claims 1-3, characterized in that the compound of the formula CHCH, / 2 \ / \ CH CH — CH, —N — CH, —CH CH IIIIIII CH CH, C = 0 CH, CH H \ CH 2 is epoxidized by reaction with epoxidizing agents. 5. FOrfarande enligt nagot ax patentanspraken 1-3, kdnnetecknat clarav, att foreningen med formeln CH2 ,/ \/ CH2\ CH CH—CH,—NH—CH,—CH CH IIIIII CH CH, C=O CH, CH CH41123 epoxideras genom omsattning med epoxiderande medel.5. A process according to any one of claims 1-3, characterized in that the compound of the formula CH2, / / / CH2 \ CH CH-CH, -NH-CH, -CH CH IIIIII CH CH, C = O CH, CH CH41123 is epoxidized by reaction with epoxidizing agents. 6. Forfarande enligt patentanspraket 1, kannetecknat darav, att foreningar med den allmanna formeln R. R,R, R, '\ R3iC \Rg Ft2\ /C\ /R2 C C—CH,—N—Z—N—CH,—C C X Y CC' \ /\ / R4 C/ R, /\ R, R, van i R1, R99 B,, R49 R59 R6, R7, Rg, Re, X, Y och Z ha den i patentanspraket 1 angivna betydelsen, epoxideras genom omsattning med epoxiderande medel. / \R _7u /\ R, R,6. A process according to claim 1, characterized in that compounds of the general formula R 1 R 2, R 3, R 3, R 3, R CCXY CC '\ / \ / R4 C / R, / \ R, R, van in R1, R99 B ,, R49 R59 R6, R7, Rg, Re, X, Y and Z have the meaning given in patent claim 1, epoxidized by reaction with epoxidizing agents. / \ R _7u / \ R, R, 7. Forfarande enligt nagot av patentanspraken 1-6, kdnnetecknat darav, att foreningar med den allmanna formeln CH,CH2 / \/ \ HC CH—CH,—N—Z—N—CH,—CH CH IIIIIIII HC CH—R X Y R'—CFI CH \' CH,/\ r-F4 / ,A. 1 2 van i X, Y och Z ha den i patentanspraket 1 angivna betydelsen och R' och R vardera betecknar en vateatom eller en lagmolekylar alkylrest, epoxideras genom omsattning med epoxiderande CH,CH / \/ 2\ CH CH—CH,—N—CH,—CH,—N—CH,—CH CH IIII C=0 CH, CH u....L2 Anforda publikationer: Stockholm 1962. liungl. Boktr. P. A. Norstedt & &incr. 620089 CH CH2 C=0 CH,CH3 epoxideras genom omsattning med epoxiderande medel. medel.7. A process according to any one of claims 1-6, characterized in that compounds of the general formula CH, CH 2 / \ / \ HC CH — CH, —N — Z — N — CH, —CH CH IIIIIIII HC CH — RXY R '—CFI CH \' CH, / \ r-F4 /, A. 1 2 van in X, Y and Z have the meaning given in patent claim 1 and R 'and R each represent a hydrogen atom or a lower molecular weight alkyl residue, epoxidized by reaction with epoxidizing CH, CH / \ / 2 \ CH CH-CH, -N —CH, —CH, —N — CH, —CH CH IIII C = 0 CH, CH u .... L2 Request publications: Stockholm 1962. liungl. Boktr. P. A. Norstedt & & incr. 620089 CH CH 2 C = O CH, CH 3 is epoxidized by reaction with epoxidizing agent. average. 8. FOrfarande enligt nagot ax patentanspraken 1, 6 och 7, kannetecknat darav, att foreningen med formelnA method according to any one of claims 1, 6 and 7, characterized in that the compound of the formula