DE1720403A1 - New polyglyeidyl compounds containing urethane groups, processes for their preparation and use - Google Patents

Description

Dr. F. Zumsfein - tyt. S. Assnionn

Df, R.Koen? J ^ ÄBeri! ^; Dipl. Phys. R. Holzhauer

Munich 2, Brauhausstrafje 4 / ll |

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Case 5970 / E

Germany

New polyglycidyl compounds containing urethane groups, processes for their production and application.

The present invention relates to polyglycidyl compounds, which, when hardened with hardeners for epoxy resins, result in elastic moldings.

The inventive polyepoxides correspond to formula

109832/1640

(I)

«O-A-:

21-1

-O — C-NH-

NH-CO-X-

-R

where η is an integer of at least 2, preferably 2 or 3, X is an oxygen or sulfur atom, R is an n-valent aliphatic radical which can be interrupted by oxygen atoms, sulfur atoms and carboxylic acid ester groups and R _{1 is} an aliphatic radical with a terminal 1, 2-epoxy group, which can be substituted by halogen atoms or interrupted by oxygen or sulfur atoms, but is preferably a 2,3-epoxypropyl group, A is the radical of a glycol, a polyglycol, thiodiglycol or poly (thiodiglycol), of which the terminal Hydroxyl groups have been removed, ra = 1 or 2, and p = 1 or 2, preferably = 1.

The new polyepoxides containing urethane groups can be obtained according to the invention by adding a urethane pre-adduct the general formula

(II)

NH-CO-X-

-R

η
where η is a whole _; Number of at least 2, preferably 2 or 3, X is an oxygen or sulfur atom, R is an n-valent aliphatic radical which can be interrupted by oxygen atoms, sulfur atoms and carboxylic acid ester groups,

1 0S832 / 16A0

BATH ORIGINAL

with a 1,2-epoxy alcohol of the formula

converts, in which R, is an allphat! shear radical with a terminal 1,2-epoxy group substituted by halogen atoms or be interrupted by oxygen or sulfur atoms can, but is preferably a 2,3-epoxypropyl group, A the remainder of a glycol, a polyglycol of thiodiglycol or the poly (thiodiglycol) of which the terminal Hydroxyl groups have been removed, m = 1 or 2, and p = 1 or 2, preferably = 1.

The starting compounds (II) belong to the known class of urethane prepolymers ("urethane prepolymers") of the representatives are commercially available, and are made by adding a polyalcohol R (GH) to η mol of toluene-2,4-diisocyanate won.

Suitable polyalcohols R (OH) are preferably glycols, such as ethylene glycol, propane-l, 3-diol, propane-l, 2-diol, 2-butene-1,4-diol, Bis (4-hydroxybutyl) ether, propane-1,3-diol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, pentaerythritol and Polyglycols such as diethylene glycol, triethylene glycol, dipropylene glycol and the higher polyglycols, such as the liquid and solid polyethylene glycols, polypropylene-1,2- or 1,3-glycols, Copolymers of ethylene oxide and propylene oxide, oxetane or tetrahydrofuran, poly (butylene-1,4-glycol), poly (hexylene-1,6-glycol) as well as poly (propylene-1,2-glycol), in which the terminal secondary hydroxyl group may also pass through

'10,983 2/164 0

.'ORIGINAL INSPECTED

Addition of ethylene oxide to a primary hydroxyl group has been converted.,

As long-chain starting compounds of the formula R (OH) can also serve polyacetals with terminal hydroxyl groups, which by copolymerization of alkylene oxides, such as Ethylene oxide or propylene oxide can be obtained with formaldehyde or trioxane, or from aldehydes, in particular formaldehyde, and alcohols, whose hydroxyl groups are obtained by at least 4 Carbon atoms are separated from each other, such as butane-1,4-diol, Pentane-l, 5-diol, hexane-l, 6-diol and decane1,10-dlol, arise ^

R (OH) are also very good starting compounds long-chain linear polyesters with terminal hydroxyl groups, which are derived from the acid components oxalic acid, malonic acid, Succinic acid, glutaric acid, methyl adipic acid, sebacic acid, diglycolic acid, methylene-bis-thioglycolic acid, / ', ^' - sulfo-dibutyric acid, Thiodibutyric acid, phthalic acid, isophthalic acid, terephthalic acid and especially adipic acid, as well as from the Glycol components di-, tri- and polyethylene glycol, propane-1,2- and 1,3-diol, butane-1,4-, 1,3- and 2,3-diol, hexane-1,6-diol, Decane-l, 10-diol, octadecane-l, 12-diol, 2,2-dimethylpropane-l, 3-diol, Glycerol monomethyl ether and, in particular, ethylene glycol.

For the synthesis of the compounds (II) suitable polyols (II), which at the same time contain sulfide groups, are by Use of thioglycol, polyglycols based on thioglycol and polyesters based on thioglycol, which end-

1038 32/1640

ORIGINAL INSPECTED

carry permanent, primary hydroxyl groups. Instead of thiodiglycol one can also use bis (4-hydroxybutyl) thioether use.

Urethane pre-adducts (II), in which X represents a sulfur atom, are obtained by using dithiols, such as ethylenedithiol, propylene-1,200thiol and decane-1,110-dithiol, but in particular unbranched polymeric disulfides with terminal thiol groups, which in the addition A thlocarbamate group forms on the isocyanate group in the 4-positioni suitable higher molecular weight dithiols and polythiols are the polymers of ethylene sulfide or 1,2-propylene sulfide and thlocols with terminal thiol groups, in particular technical, liquid polysulfide condensates which are obtained from high molecular weight condensates by reductive splitting $ - and having Bl & r (butyleneoxy) -gruipen Further, one can lyglykolen to the terminal primary hydroxyl groups of P _o, anneal ethylene sulfide or 1,2-propylene sulfide; bis (ethyleneoxy) methane, bis (butyleneoxy) methane, BJs (äthylenox. , whereby terminal 2-mercaptoethyl or -propyl groups are obtained Other suitable long-chain dithiols e are polyglycols esterified on both sides with mercaptoacetic acid, ß-mercaptopropionic acid or 3-mercaptobutyric acid,

When η is greater than 2, branched polyethers, polythioethers and polyesters are also suitable as starting materials R (OH) for the polyisocyanates (II). They are obtained by using polyalcohols in addition to glycols in the

109832/1640

-β- 172G4Q3

Making the polyglycols, or by using Polyhydroxy compounds as initiators in the polymerization of alkylene oxides, such as ethylene oxide and propylene oxide. Suitable polyhydroxy compounds are glycerol, pentaerythritol, sorbitol, mannitol, hexane-1,2,6-triol and trimethylolpropane. Similarly, branched polyesters containing only terminal hydroxyl groups can be used.

Those technical, commercially available urethane pre-adducts can also be used as starting products are, the partially converted toluene-2,4-disocyanate radicals and correspond to the formula (II), products whose content of isocyanate groups also come into consideration has dropped slightly due to the effects of moisture during storage. The polyisocyanates (II) are made by combining of η mol of toluene-2,4-diisocyanate with 1 mol of the n-valent polyol or polythlol of the formula R (XH) below received mild conditions.

Low molecular weight compounds, such as the homologues of glycidol, are initially used as monoepoxy alcohols (III) and especially the glycidol itself. Also suitable are the monoglycidyl ethers of diols, such as ethylene glycol monoglycidyl ethers, Propane-1,3-diol-mono-glycidyl ether, butane-1,4-diol-monoglycidyl ether, pentanediol-liS-monoglycidyl ether, Hexane-l, 6-diol-monoglycidyl ether and 3-cyclohexenedimethanol-l, l-monoglycidyl ether, as well as diethylene glycol monoglyoidyl ether, Propane 1,2-diol monoglycidyl ether and butane 1,3-diol monoglycidyl ether.

109839/1640 ORIGINAL INSPECTED

1720 (03

According to a particular embodiment of the invention, the technical mixtures obtained in the preparation of the monoglycidyl ethers of the glycols are used _; and which, depending on the method of preparation, can also contain a larger proportion of the free glycols, or preferably contain a larger proportion of the diglycidyl ethers of the glycols. In addition to the low molecular weight technical monoglycidyl ethers of the glycols, the high molecular weight monoglycidyl ethers of the abovementioned polyglycols, which are obtained by reacting about 0.5 mol to about 2.5 mol of epichlorohydrin with one of the unbranched polyglycols mentioned above, are also of particular interest Technical monoglycidyl ethers for building up the diglycidyl ethers prepared according to the invention, the end product contains the bisglycidyl ether of polyglycol as an accompanying mixture component.

It is also possible to start from monoepoxy alcohols (III) which _{carry a - S-eH 2} -CHp group, such as 2- (2 ', 3 ^I -epoxypropylmercapto) ethanol. Ä

The addition of the epoxy alcohols to those in the 2-position The isocyanate groups of the polyisocyanates (II) present are carried out by prolonged heating to moderate temperatures. Man however, the addition of the alcoholic hydroxyl group in a known manner by adding basic compounds, especially tertiary amines, such as triethylamine, pyridine, methylpyridine, Ν, Ν'-dimethylpiperazine, Ν, Ν-dimethylaminocyclohexane and accelerate N, N'-endoethylene piperazine,

10983? / 164 0

17204Ö3

however, if exothermic reactions occur for must ensure the dissipation of the heat of reaction. Other catalysts are metal salts, such as EiSOn- (III) -ChIOrId, Zinc chloride, tin (II) chloride, tin octoate, acetylacetonates, such as iron and zinc acetylacetonate, and dibutyltin dilaurate and molybdenum glycolate. The majority of the products are viscous resins.

The inventive polyepoxides react with the common hardeners for epoxy compounds. They can therefore be made analogous to other polyfunctional ones by adding such hardeners Crosslink or harden epoxy compounds or epoxy resins. As such hardeners come basic or in particular acidic compounds in question.

The following have proven to be suitable: amines or amides, such as allphatic and aromatic primary, secondary and tertiary Amines, e.g. m-phenylenediamine, p-phenylenediamine, bis- (p-aminophenyl) sulfone, Bis (p-aminophenyl) methane, ethylenediamine, hexamethylenediamine, trimethyl! Hexamethylenediamine, N, N-diethylethylenediamine, Diethylenetriamine, tetra (oxyethyl) diethylenetriamine, triethylenetetriamine, N, N-dimethylpropylenediamine, Bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) dimethyl methane, 3- (jtoinomethyl-3 * 5 * 5-trimethylcyolohexylamine, Mannich bases, such as 2,4,6-tris (dimethylaminoraethyl) phenolj Dicyandiamide, urea-formaldehyde resins, melamine-formaldehyde resins Polyamides, e.g., those made from aliphatic polyamines and dimerized or trimerized unsaturated fatty acids; more-

109837/16 40

Valuable phenols, e.g. resorcinol, bis (4-oxyphenyl) dimethyl methane, phenol-formaldehyde resins, products of conversion of aluminum alcoholates or phenolates with tautomeric react with compounds of the acetoacetate type, Friedel-Crafts catalysts, e.g. AlCl ,, SbCl ₁ - J, SnCIh, ZnCIg, BF, and their complexes with organic compounds, such as BF, -amine complexes, metal fluoroborates, such as zinc fluoroborate, phosphoric acid; Boroxines such as trimethoxyboroxine.

Polybasic carboxylic acids are preferably used as hardeners and their anhydrides, e.g. phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, Methylendomethylenetetrahydrophthalic anhydride (* methylnadlcanhydride), hexaehlorendomethylenetetrahydrophthalic anhydride, Succinic anhydride, adipic anhydride, maleic anhydride, allyl succinic anhydride, Dodecenyl succinic anhydride; 7-Allyl-bicyclo- (2.2.l) -hept-5-en2,3 - dioarboxylic acid anhydride, Pyromellitic dianhydride or mixtures of such anhydrides. One uses hardening agents which are preferably liquid at room temperature.

You can optionally accelerate such as tertiary Amines, their salts or quaternary ammonium compounds, e.g. tris (dimethylaminomethyl) phenol, benzyldlmethylamine or benzyldimethylammonium phenolate, tin salts of carboxylic acids, such as tin octoate or alkali metal alcoholates, such as e.g. also use sodium hexoxide.

1 0 9.83 "? / 1640

As a rule, however, the use of such accelerators is not necessary, and this is a special one Advantage of the novel polyepoxide compounds according to the invention compared to most known cycloaliphatic polyepoxide compounds.

When curing the polyepoxides according to the invention with anhydrides, it is expedient to use 1 gram equivalent Epoxy groups 0.5 to 1.1 gram equivalent anhydride groups.

Optimal properties of the cured products are usually obtained when using 1 equivalent of anhydride groups per equivalent of epoxy groups. If an accelerator containing hydroxyl groups is used, however, there is an increase the added amount of anhydride hardener is expedient.

The term "hardening" as used herein means the conversion of the above polyepoxides into insoluble ones and infusible, crosslinked products, usually with simultaneous shaping into shaped bodies, such as Castings, pressed bodies or laminates or flat structures such as lacquer films or bonds.

The present invention therefore also provides curable mixtures which contain the polyepoxides according to the invention, optionally together with other di- or polyepoxy compounds and also curing agents for epoxy resins, such as preferably Di- or polyoarboxylic anhydrides contain.

ORIGINAL INSPECTED 10983 ?. / 1640

The inventive polyepoxy compounds or their mixtures with polyepoxy compounds and / or hardeners can also be filled with fillers in any phase prior to hardening, Plasticizers, pigments, dyes, flame retardants, mold release agents are added.

Asphalt, bitumen, glass fibers, cellulose, mica, quartz powder, Aluminum oxide hydrate, gypsum, kaolin, ground dolomite, colloidal silicon dioxide with a large specific upper w surface (AERGSIL) or metal powder such as aluminum powder will.

The curable mixtures can be in the unfilled or filled state, optionally in the form of solutions or Emulsions, as textile auxiliaries, coating agents, laminating resins, Paints, varnishes, dipping resins, casting resins, molding resins, molding compounds, coating compounds and leveling compounds, flooring compounds, Embedding and insulation compounds for electrical engineering, adhesives and for the production of such ~ Products serve.

Preparation of the glyeidyl ethers used as starting materials in the examples , containing hydroxyl groups, or the mixtures containing such glycidyl ethers.

The pressure is given in Torr. The values given for epoxy equivalents / kg are based on the method described by A.J. Durbetaki in "Analytical-Chemistry", Vol. 28, No. 12, December 1956,,

Pages 2000 - 2001, described method with hydrogen bromide determined in glacial acetic acid. 10983? / 1640

I. Production of butane-1,4-diol monoglyoidyl ether

A. Manufacture of the raw product .

A mixture of 1080 g: (12 mol) 1,4-butanediol and 3336 g (36 mol) epichlorohydrin was poured into a 6-liter flask equipped with a stirrer, reflux condenser, internal thermometer and a closable nozzle for the portion-wise addition of the sodium hydroxide warmed to about 65 ° C using a heating bath. Within about 1 1/2 hours, a total of 540 g (13 * 2 mol) of sodium hydroxide (about 98%) divided into 10 equal portions were added in portions; The outside temperature is initially maintained at about 70 ° C was reduced initially to about 40 ° C and towards the end of the Natriumhydroxydzugabe to 30 ⁰ C. The next portion of sodium hydroxide was added when the heat development of the previous portion had subsided so that the internal temperature was again about 60 ° C. After the addition of the sodium hydroxide had ended, an azeotropic mixture of epichlorohydrin and water of reaction was distilled off on the descending condenser, the distillation temperature being about 110.degree. After cooling to room temperature, the precipitated NaCl was filtered off and the salt was washed with a little epichlorohydrin. The excess epichlorohydrin was distilled off from the combined filtrates via a Vigreux column, initially at a pressure of about 120 torr, and towards the end at about 12 torr the inside temperature was about 120 ° C, the outside temperature was 125 ° C. As a KoI

109832/1640

The residue obtained 1850 g of a brown, clear liquid with low viscosity, which is referred to below as the crude product.

B. Production of pure butane-l ^ -diol-monoglycldyl ether.

The 1850 g of crude product were over a Claisen attachment Crude distilled on the descending condenser at about 0.1 torr until the distillation temperature was about 180 ° C. One received about 1350 g of a colorless, clear distillate with low Viscosity. The flask residue was about 480 g.

The 1350 g of the distillate were subjected to fractional distillation on a long column coated with wire mesh rings made of stainless steel and carrying a diplegmator. The portions passing over at a distillation temperature of about 80 ° C. and a pressure of about 0.01 torr, as long as they had a value of 6.7 to 6.85 epoxy equivalents / kg, were collected separately. 580 g of a (based on the gas chromatogram) 98.0% butanediol-1-4 monoglyeidyl ether were obtained. It contained 6.77 (theory 6.84) epoxy equivalents / kg.

Calculated ; for G ₇ H ₁ ^ O ₃ · Molecular Weight .: 146.18 Found

C 57.51 % C 57.71 %

H 9.65 % H 9.65 %

0 32.84 % 0 33.14 %

C. Technical butanediol monoglycidyl ether »

Analogous to that described for the production of the crude product Procedure were, starting from 405 g

10 9837/1840

(4.5 moles) butane-1,4-diol, 1250 g (13.5 moles) epichlorohydrin and 202 g NaOH (98 # Lg) [4.95 mol], 640 g one of epichlorohydrin obtained freed crude product. This became, without prior crude distillation on the column, as in the isolation of butanediol 1,4-raonoglycidyläther which low-boiling initial fractions with a high epoxy content (15 g) removed. The sum of the following fractions (until the Content of epoxy equivalents / kg after reaching a maximum from 9.0 to 9.88 began to decrease again) gave 402 g of technical-grade butanediol-1,4-monoglycidyl ether. This had a salary of 6.7 epoxy equivalents / kg and contained a larger proportion of the diglycidyl ether of 1,4-butanediol and also still a little 1,4-butanediol.

II. Production of hexanediol-1,6-monoglycidyl ether.

First of all, a 2.5 liter flask equipped with a stirrer, internal thermometer, dropping funnel and descending condenser, which contained a mixture of 826 g of technically pure 1,6-hexanediol and 1050 g of toluene, for the purpose of removing water about 450 g of toluene were distilled off, then the mixture was cooled to an internal temperature of 50.degree. The descending one The condenser was replaced with a reflux condenser, and 7 ml of tin tetrachloride was added to the mixture. Within A total of 648 g of epichlorohydrin were added dropwise for about 70 minutes, the internal temperature was kept at 50 to 51 ° C by the bath temperature was gradually lowered from initially 50 ° C to 33 ° C and only towards the end of the epichlorohydrin

10983? / 1640

addition was increased again towards 50 ° C. They still read 15 React at this temperature for minutes and then cool down Room temperature. The dropping funnel was removed from the apparatus removed. At a bath temperature of 20 ° C., a total of 343 g of 98% sodium hydroxide were added in about 20 minutes entered small portions, the internal temperature rising to about 30 ° C. Within a further 10 minutes it became The mixture was heated to an internal temperature of 50 ° C., left at this temperature for 1/2 hour and then cooled to room temperature. The precipitated sodium chloride was filtered off and washed with toluene. The combined filtrates were volatile components in a water jet vacuum and in a distilled off to about 90 C rising bath temperature. Man obtained as flask residue 1218 g of crude product, which is the hexanediol-1,6-monoglycidyl ether contained.

The 1218 g of the crude product were over a Vigreux column at a pressure of about 0.1 Torr to a bath temperature of 240 ° C and a distillation temperature of 160 ° G distilled, · 1133 g of technical hexanediol-1,6-monoglycidyl ether were thereby obtained with a content of 5,4-epoxy equivalents per kg. The piston residue was 41 g.

1125 g of the technical hexanediol-1,6-monoglyeidylether were attached to a 35 cm column loaded with stainless steel wire mesh rings, which had a dephlegmator carried, fractionally distilled at about 0.1 torr. The proportions passing between about 80 ° C and 90 ° G were

1.09837 / 1 64 0

as long as these have a content of 5.7 to 6.0 epoxy equivalents / kg (total 270 g), collected separately. The 270 g mentioned were again fractionally distilled in the same column, the fractions which had passed over at 87 ⁰ to 93 ° C./0.01 Torr and had a content of 5 * 7 to 5 * 8 epoxy equivalents / kg were collected again separately. A total of 245 g of hexanediol-1,6-monoglycidyl ether with a content of 5.72 epoxy equivalents / kg (theory: 5.74 epoxy equivalents / kg) were obtained.

Combustion analysis;

CH ₁₈ O ₃ J Mol. Wt. 174.23

Calculated C 62.04 % H 10.41 % 0 27.55 % Found: C 62.31 % H 10.48 % 0 27.70 %

III. Production of 2,2-dimethylpropanediol-1,3-monoglycidyl ether.

280 g of a mixture containing the mono- and diglycidyl ethers, the preparation of which is described below, was at a water jet vacuum (12 Torr) on a 35 cm long column charged with stainless steel wire mesh rings, which carried a dephlegmator, fractionally distilled. Those fractions which have a content of 6.2 epoxy equivalents / kg and which distilled at 119 ° C to 120 ° C / 12 Torr (68 g in total) were collected separately. They consist of the monoglycidyl ether of 2,2-dimethylpropanediol-1,3i which following combustion analysis

109837/16 40

showed:

^c 8 ^H l6 ° 3

Calculated; C 59 * 98 % H 10.07 % ■ Found: C -60.11 % H 10.31 %

According to the gas chromatogram, the product is 98.2%. The above, the mono- and diglycidyl ethers of 2,2-dimethylpropanediol-1,3 containing mixture was obtained as follows:

In a 2.5-liter flask equipped with a condenser, stirrer, internal thermometer and closable nozzle (for the later addition of the sodium hydroxide), 312 g of 2,2-dimethylpropanediol-l, 3j 15βΟ g of toluene and 390 g of epichlorohydrin were mixed and after the addition of 3 ^m l of tin tetrachloride heated in a water bath at 40 ° C, giving a clear solution was obtained. Within about 2 1/2 hours, the bath temperature (and the internal temperature) was increased to about 48 ° C. and held at this temperature for about 2 hours, after which a further 2 ml of tin tetrachloride were added to the reaction mixture. The bath and internal temperature were held at 50 ° C. for a further 1 1/2 hours and then cooled to about 15 ° C.

At a bath temperature of 5 to 10 ° C were the reaction mixture at an internal temperature not exceeding about 25 ° C., a total of 172 g of 98% in about 10 minutes Sodium hydroxide added in portions. The internal temperature was increased to about 50 ° C. within about 1/2 hour and held at this temperature for about 20 minutes.

10 9 8 3 7/1840

It was then cooled to room temperature. The precipitated common salt was filtered off and twice with Washed out toluene. The combined filtrates were toluene and unreacted epichlorohydrin in a water jet vacuum distilled off up to a bath temperature of about 90 ° C.

512 g of a liquid, slightly brown pebble residue were obtained with a content of 5j.-3 epoxy equivalents / kg. This crude product contained the mono- and diglycidyl ethers of 2,2-dimethylpropanediol-1,3.

From 485 g of the crude product mentioned were about a Vigreux column at a pressure of about 0.1 Torr volatile components up to a distillation temperature of 90 ° C (bath temperature about 160 ° Cj internal temperature about 150 ° C) distilled off.

The distillate obtained was 290 g of colorless, clear technical 2,2-dimethylpropanediol-1,3-monoglycidyl ether a content of 7 * 4 epoxy equivalents / kg, which is a contained a larger proportion of diglycidyl ether.

In the fractional distillation of the technical-grade monoglycidyl ether, fractions which partially crystallized and thus unchanged 2,2-dimethylpropanediol-1,3 contained.

The fractions passing over after the monoglycidyl ether at 156 ° C. and 18 Torr, insofar as they have a content have from 9j14 to 9 * 28 epoxy equivalents / kg from 104 g of pure diglycidyl ether of 2,2-dimethylpropanediol-1,3.

IV. Production of diethylene glycol monoglycidyl ether

A. Manufacture of the raw product

In essence, the previously under ¹¹ I · production of butane-l ^ -diol monoglycidyl ethers "described operation was repeated.

530 g of diethylene glycol (5 mol) and 185 g of epichlorohydrin were used (20 moles) and 205 g of sodium hydroxide (5 moles). After evaporation, 786 g of crude product with 5 * 24 are obtained Epoxy equivalents / kg.

B. Obtaining diethylene glycol monoglycidyl ether.

The 786 g of the above crude product were initially at a pressure of about 0.1 torr above a Claisen attachment coarsely distilled to an internal temperature of about 160 ° C (distillation temperature about 125 ° C). 618 g of coarse distillate are obtained with 5 »8 epoxy equivalents / kg.

The named en-618 g were now at a pressure of about 0.1 Torr finely fractionated, with those fractions which has a content of 5 * 5 to 6.2 epoxy equivalents / kg had, were collected separately. The corresponding The distillation temperature range was 80 to 86 ° C. The 299 g of the Pein distillate obtained contained 6.17 epoxy equivalents / kg (the theory calls for 6,166). The gas chromatogram showed a content of 97.1 percent by weight diethylene glycol monoglyc idyl ether.

109 83? / 1 6 OK

C. Technical diethylene glycol monoglycldyl ether

As the crude product mentioned earlier via a Vigreux column distilled in a water jet vacuum and the epoxy content of the distilling components was continuously monitored, These values fell sharply at the beginning, passing through a minimum at around 3.8 epoxy equivalents / kg (distillation temperature about 130 ° C), then rose slowly and passed through a maximum at about 8.5 epoxy equivalents / kg, Die Distillation was terminated immediately after this maximum had been reached (distillation temperature 175 ° C.). From 500 g Crude product was in this way 300 g of distillate with 6.0 Obtained epoxy equivalents / kg and designated as type B coarse distillate. '

The distillation described above was repeated and discontinued when the epoxide content after passing through the minimum of about 3.8 Epoxydäquivalenten / kg again to about 5 Epoxydäquivalenten / kg (Destilliertemperatur 138 ⁰ C) had risen. The proportions distilled up to now have not been taken into account. The portions distilled from now on until immediately after passing through the maximum of about 8.5 epoxy equivalents / kg resulted in 200 g of distillate with 6.7 epoxy equivalents / kg and were designated as type A coarse distillate.

V. Production of butane-1,3-diol monoglycidyl ether

1 ml of boron trifluoride diethyl etherate was added to 500 ml of absolute toluene dissolved and 180 g (2 mol) of distilled butane-1,3-oil added. 203.5 g were added to this reaction mixture

10983 ?. / 1640

(2.2 moles) of epichlorohydrin are added dropwise in such a manner that a temperature of 67 ⁰ was maintained to 71 ° C constantly by the exothermic reaction and, if necessary by external heating. After the addition had ended, the mixture was left to post-react at 70 to 71 ° C. for 4 1/2 hours. 80 g (2 mol) of powdered sodium hydroxide were added to the cooled reaction mixture in such a way that a temperature of 40 ° C. was always maintained as a result of the exothermic reaction. After the addition had ended, the mixture was left to react for 40 minutes at the same temperature. It was then filtered and distilled. The fraction over the boiling interval from 60 ° C / 0.09 Torr to 79 ° C / 0.09 Torr had a hydroxyl equivalent weight of β2.0 and an epoxy equivalent weight of 138.5 and weighed 14o g.

This crude product, still butane-1,3-diol, butane-1,3-diol diglycidyl ether as well as mainly containing the two isomeric butane-1,3 "diol monoglycidyl ether, was direct used for epoxy resin production.

9837/164

-22- 17 2 O A O 3

174 g of toluene-2,4-diisocyanate were mixed with 206 g of polyethylene glycol rait the average molecular weight 412 (average hydroxyl equivalent weight 206) added, with weak exothermic reaction occurred. The reaction mixture was initially weak with stirring and exclusion of moisture Cooling, after the exothermic reaction has subsided, kept at 35 ° to 40 ° C. by additional heating until the isocyanate equivalent weight is between 370 and 390, which after approx. 2 1/2 to 3 hours applied. The course of the reaction was determined by repeatedly determining the isoyanate equivalent by titration of the excess of a given amount of di-butylamine solution [according to E. Müller, in Houben-Weyl, Methods of Organic Chemistry, 4th Edition 14/2, page 85 (1961] Monitored.

To 380 g of the isocyanate pre-adduct obtained above with an isocyanate equivalent weight of 380 was 147 g 98.0% butane-1,4-dlol monoglycidyl ether added and for so long heated to 40 ° C until no isocyanate content was found any more could be, which took about 10 hours.

A viscous epoxy resin with a content of 2.0 epoxy equivalents / kg was obtained, which mainly from the compound of the formula

ORIGINAL INSPECTED 1098 3 7/1640

where G, which freed from the terminal hydroxyl groups The remainder of a polyethylene glycol is HO-G, -OH with an average molecular weight of 412; consists.

The epoxy resin obtained was treated with hexahydrophthalic anhydride cured hot. The samples had the following mechanical properties:

Tensile strength according to VSM 77 101 = 1.9 kg / mm ² elongation at break "" 77 101 = 70 %

Example 2

56.7 g polybutylene glycol with the average molecular weight 654 (mean hydroxyl equivalent weight 327) mixed with 30 * ^ g of toluene-2,4-diisocyanate, one weak exothermic reaction occurred. The reaction mixture was then stirred and with exclusion of moisture as long as heated to 70 ° to 80 ° C until only 1.95 up to 2.05 isocyanate equivalents / kg according to the titration according to the example 1 was detectable, 51.3 ß of the viscous product obtained with an isocyanate equivalent weight of 513 were with 1 ^, 7 g of 98, l # igem butane-1,4-diol-mono-glycidyl ether added and heated to 60 ° to 70 ° C until no isocyanate content more was noticeable, which took about 4 to 5 hours. It was an epoxy resin with a content of 1.46

10983? / 16 / * 0

L INSPECTED

Epoxy equivalents / kg obtained, which mainly consists of the compound of the formula

₂ -) jO-CO-NH NH-a0-0-fCH ₂ -) ^ - _{O-CH 2} -CH-CH

in which G _{2 is the radical of the polybutylene glycol HO-G 2} -OH with an average molecular weight of 654, which has been freed from the terminal hydroxyl groups.

After curing with 2 ₁ 2,4-trimethyl-l, flexible body gummielestische 6-diaminohexane were obtained.

Example 3

174 g of toluene-2,4-diisocyanate were mixed with 490 g of polybutylene glycol with an average molecular weight of 98Ο (average Hydroxyl equivalent weight 490) added, with a weak exothermic reaction occurred. The reaction mixture was kept at 30 ° C. with exclusion of moisture and stirring until the isocyanate equivalent weight was between 65Ö and 670, which was reached after about 3 1/2 to 4 hours.

To 664 g of the pre-adduct obtained above with a leocyanate equivalent weight of 666, 146 g of 98% were added Butane-1,4-diol monoglyyl ether added and while under Stirring heated to 50 ° C until no more isocyanate content detected could be. A viscous epoxy resin with a content of 1.28 epoxy equivalents / kg was obtained, which mainly from the compound of the formula

109837/16 ^ 0

ORiGiNAL iMSPECTBD

O-3H ₂ -CH-CH ₂ -0-fCH ₂ -) j-0-C0-HN "

NH-CCMD-G

p-co-o-fcH ₂ ^ o-cH ₂ -cH - σ

wherein G_ freed from the terminal hydroxyl groups The remainder is ^ eiTPolybutylenj ^^ with an average molecular weight of 980.

example

174 g of toluene-2,4-diisocyanate were mixed with 220 g of polypropylene glycol with the average molecular weight 440 (average hydroxyl equivalent weight 220) added, with exothermic Reaction occurred. The reaction mixture was initial by weak cooling, after the exothermic reaction has subsided by additional heating with stirring and exclusion of moisture held at 40 ° to 50 ° C until the isocyanate equivalent weight was between 38Ο to 400, which is roughly Required 4 hours.

To 393 g of the product obtained above with an isocyanate equivalent weight of 390 were 146 g of 98il ^ iger butane-1,4-diol monoglycidyl ether added and heated to 50 ° C with stirring until no isocyanate content was detectable, which required about 6 hours. It became a yellowish, viscous epoxy resin with a content of 2.12 epoxy equivalents / kg, which mainly consists of the compound of the formula

i ₂ -GH-GH ₂ -O-fGH ₂ -HO-GO-NH NH-CO-O-fCH, '

■.-O-GO-NH

wherein G _1, freed of the remaining terminal hydroxyl groups of the polypropylene glycol HO-G ^ -OH having the average J _> n molecular weight of 440 is composed.

The epoxy resin obtained was cured while hot with hexahydrophthalic anhydride. The samples had the following mechanical properties:

Tensile strength according to VSM = 2.4 kg / mm elongation at break according to VSM = 77 %

Example 5

394 g of polyethylene glycol with an average molecular weight of 874 (average hydroxyl equivalent weight 437) were 157 g of toluene-2,4-diisocyanate were added. With stirring and exclusion of moisture, it initially became weak exothermic reaction, the reaction mixture is allowed to react at 40 ° to 50 ° C., the isocyanate equivalent weight calculated in advance from 590 to 610 was reached after approx. 5 hours.

For this pre-adduct obtained with an isocyanate equivalent weight of 598 were 134 g of 98.0% strength butane-1,4-diol monoglycidyl ether added and the reaction mixture heated to 50 ° to 60 ° C until there is no more isocyanate content.

1 0 3 H 3 9/1 ft A 0 _ ^ _a , _{s iri} ^ .. _. ^. _Γι

could be shown, which took about 8 hours. It was a waxy epoxy resin with a content of 1.63 epoxy equivalents / kg obtained, which mainly from the compound of the formula

CH -GH-OH -O-fCH ₂ ^ -0-G0-NH

wherein G is the radical of the polypropylene glycol HO-G, - OH with the middle one, freed from the terminal hydroxyl groups

t ■> A , ., ■■ - ■■ - ■■■

~ " ^K molecular weight of 87 ^ 1st, consists.

Example β

? 2.1 g "ADIPREN L-100" (hand product of the company DuPont, Wilmington, Del., U.S.A., an adduct of polybutylene glycol and tolylene diisocyanate), which by absorption of water only an isocyanate content of 1.39 isocyanate equivalents / kg had, was with 16.5 g of distilled 2,2-dimethyl-propanediol-l ^ -monoglycidyl ether (98.2%) added and heated to 70 ° C until no isocyanate content was more detectable.

The total reaction time was 4 to 5 hours. It became a yellowish, waxy epoxy resin with a Obtained epoxy content of 1.17 epoxy equivalents / kg.

When the resin was cured with hexamethylenediamine, flexible, notch-resistant cast bodies were obtained.

- ₂₈ . 1720 / .03

Example 7

320 g of the polyethylene glycol used in Example 1 with an average molecular weight of 412 (average hydroxyl equivalent weight 206) were mixed with 278.5 g of toluene-2,4-diisoT cyanate, an exothermic reaction occurring immediately. The temperature was kept between 30.degree. And 35.degree. C. by cooling. After the exothermic reaction had subsided, the mixture was held for a further hour at 30.degree. C. During the reaction, the isocyanate content fell from 5.2 and 2.6 lenten / kg The mixture was then heated to 80 ^° C. and then 118.5 g of glycidol were added dropwise over the course of 15 minutes. After the addition had ended, the reaction mixture was held for a further 2 hours.

Sixteen g of a highly viscous epoxy resin were obtained ten, which had a content of 2.7 epoxy equivalents / kg. It mainly consists of the connection of the formula

0

CH, r CH-CH ₀ -O-GO-KH ffii-CO-O-CH.-OH-CH ₀

2 ι ι 2 2

where G, the radical of a polyether, freed from the terminal hydroxyl groups, with the average molecular weight 412 is.

10383? / 1-6 40

ORIGINAL INSPECTED

Example 8

350 g of the polybutylene glycol used in Example 3 and having an average molecular weight of 980 (average hydroxyl equivalent weight 490) were admixed with 121.8 g of toluene-2,4-diisocyanate. The temperature was kept between ^30.degree. And 35.degree. C. by cooling. After the exothermic reaction had ended, the mixture was left to react at 30 ° C. for a further hour. Then 0.2 g of triethylamine was added and 52 g of glycidol were added dropwise over the course of 20 minutes with stirring. After the addition of glycidol, the reaction was exothermic for a further 2 hours. After cooling, 523 g of a pale, viscous resin were obtained which had a content of 1.34 epoxy equivalents / kg and; practically no more isocyanate content. It consisted mainly of the diepoxide of the formula

^^^^ racooG ^

where G ₇ . freed from the terminal hydroxyl groups. Is the residue of a polybutylene glycol with an average molecular weight of 980.

109337/164

Example 9

To 200 g of absolute chlorobenzene, 24.8 g (0.4 mol) of freshly distilled ethylene glycol and 139.0 g (0.8 mol) Given toluylene-2,4-diisocyanate. This resulted in an exothermic reaction which was kept at 35 to 37 ° C. with weak cooling could be. After about 1 hour the reaction mixture was homogeneous. The course of the reaction was determined by repeated determination the isocyanate equivalent weight of the reaction mixture, tracked. When the value approached the calculated limit of (consumption of half of all isocyanate groups), 147.5 grams (0.8 hydroxyl equivalents) of hexamethylene glycol monoglycidyl ether of 95, l # iger purity with an epoxy equivalent weight of 171 and a hydroxyl equivalent weight of 185 was added. The temperature in the reaction mixture was then held at 40 ° C. for 4 hours and at 50 ° C. for 7 hours. Then no more isocyanate groups could be detected. For work-up, all of the chlorobenzene was used at the end Evaporated under high vacuum, the product was a yellow epoxy resin which no longer flowed at room temperature a content of 2.86 epoxy equivalents / kg. It consists mainly of the compound of the formula

52.3 g of the epoxy resin thus obtained were mixed with 133 g \ 4-tetrahydrophthalic acid diglycidyl ester with an epoxy

1098 3 9/1640

content of 6.4 epoxy equivalents per kg heated to 50 ° C and with 59% technical grade trimethyl / hexamethylenediamine [Isomer mixture of 2,4,4-trimethyl- and 2,2,4-trimethylhexamethylenediamine] well mixed. After a short vacuum treatment to remove the air bubbles, the mixture became in Preheated Zugkö'rperforms cast and subjected to a heat treatment for 3 hours at 90 ° C. On the traction bodies the following properties were measured:

Tensile strength according to VSM = ^ 50 kg / on elongation at break "" = 4 %.

Example 10

In 200 g of absolute chlorobenzene, 47.2 g (0.4 mol) Suspended hexamethylene glycol and 139 * 0 S (0.8 mol) of toluene-2i4-diisocyanate added. The suspension obtained was heated to 33 ° C. with vigorous stirring and by repeated determination the isocyanate equivalent weight of the course of the reaction supervised. After an isocyanate equivalent weight of 484 had been determined, 14y, 5 6 (0.8 hydroxyl equivalent weight) Hexamethylene glycol monoglycidyl ether from 95% Purity and an epoxy equivalent weight of 171 * one Hydroxyl equivalent weight of 185 and 200 g absolute chlorobenzene added. The reaction mixture reacted slightly exothermically after the addition and was then externally Heating brought to 40 ° C. Only as the reaction progresses

■ Ί 09839/1 6- £ Q '■' ..

_ ₃₂ . - 17 2 U Λ Ο 3

a homogeneous solution was obtained. After a post-reaction of 6 hours at 40 ° C. and 5 hours at 50 ° C. there were none Isocyanate groups more detectable. The reaction mixture was concentrated and finally at 80 ° C / 0.005 Torr to wt cht constancy brought. A viscous, yellow-colored epoxy resin with a content was obtained in quantitative yield of 2.52 epoxy equivalents / kg. It consists in the Mainly from the compound of the formula

396 g of the epoxy resin thus obtained were heated to 80.degree and mixed well with 99 g of 4,4'-diaminodiphenylmethane. After removing the air bubbles, the mixture was in preheated Tensile body molds cast and a heat treatment during l6 Subjected to hours at 100 ° C. The following were used on the traction bodies Strength values measured:

Tensile strength according to VSM> 642 kg / nm ² elongation at break "" ** ._. . 4 %

10983

Example 11

In 200 g of absolute chlorobenzene, 48.8 g (0.4 mol) Suspended thiodiethylene glycol and 139.0 g (0.8 mol) of toluene-2,4-diisocyanate added. The resulting suspension was heated to 36 to 37 ° C. with stirring, whereby the reaction mixture became homogeneous after about 25 to 30 minutes. The course of the reaction was determined by repeated determination of the isocyanate content of the reaction mixture monitored. After the Isocyanate content had dropped to half and the The calculated isocyanate equivalent weight of 484 approached, at an isocyanate equivalent weight of 462, 129.5 g (0.8 mol) diethylene glycol monoglycidyl ether (98.6%) added. The reaction mixture was then 4 hours heated to 40 to 41 ° C and 2 hours to 50 to 51 ° C. Then no isoyanate groups were detectable any more. As a result, the chlorobenzene was evaporated and the epoxy resin at 60 ° C bath temperature and 0.005 Torr concentrated to constant weight. In quantitative yield, it became a highly viscous ice cream yellow product with a content of 2.36 epoxy equivalents / kg obtain. It mainly consists of the

Compound of Formula 0

^ - σΗ-σΗ ₀ -ο-σ ₀ Η.-ο-σ ₀ Η, -ο-σο-Μ

10 9 83 7/16 4

42.3 g of the epoxy resin thus obtained were 15 * 4 g Hexahydrophthalic anhydride heated to 80 ° C and mixed well. After a heat treatment for 16 hours at At 100 ° C., a hard molding material of high toughness and good adhesion to glass would be obtained.

Example 12

In 400 g of chlorobenzene, 204.5 g (0.32 hydroxyl equivalents) of a hydroxyl-containing polyester (manufactured according to the usual esterification process from 4 moles of sebacic acid and 5 moles of hexane-1,6-diol with a hydroxyl equivalent weight von 637) at 55 ° C. and cooled to 25 ° C. The ester crystallizes again on cooling partially off. Then 55 * 6 g (0.32 mol) of toluene-2,4-diisocyanate were added added, whereupon the reaction mixture soon became homogeneous with an exothermic reaction. Under ice cooling was kept the temperature at 36 to 37 ° C. The course of the reaction could be monitored by repeatedly determining the isocyanate content. As the isocyanate equivalent weight of the reaction mixture to the calculated value of 2060 (isocyanate equivalent weight of the reaction mixture in which only half of the isocyanate groups used were still present) approached, 48.2 g (0.32 hydroxyl equivalent) of 95.8 # strength butane-1,4-dlol monoglycidyl ether (epoxy equivalent weight 146.0j hydroxyl equivalent weight 150.5) added. Then became Post-react for 3 hours at 40 ° C and 5 hours at 50 ° C

left, whereupon the isocyanate content was no longer detectable. After concentration, at the end below 0.01 Torr at 90 ° C bath temperature, was a solid, light brown epoxy resin at room temperature with a content of 1.12 epoxy equivalents / kg obtain.

893 g of the epoxy resin were heated to 80 ° C and with 42.5 g of 3- (aminomethyl) -3.5 # i> -trimethyl-cyclohexylamine were mixed well. After a brief vacuum treatment to remove the air bubbles, the mixture was poured into preheated tensile body molds and a heat treatment for 16 hours at 100 ° C subject. The following strength values were measured on the tensile bodies:

ρ tensile strength according to VSÄ = 1.00 kg / mm elongation at break "" * 200 % .

10983? M RiO

! MSPSCTED

Example 13

Analogously to the process described above, 80.3 g (0.44 hydroxyl equivalents) of a hydroxyl group-containing were added to 400 g of chlorobenzene Polyester (produced by the usual esterification process from 4 moles of adipic acid and 8 moles of butane-1,4-diol with a hydroxyl equivalent weight of 18 l) at 37 ° C and added 77.4 (0.44 mol) of toluene-2,4-diisocyanate. Just before the isocyanate equivalent weight of the reaction mixture had reached the calculated amount of 1256 72.0 g (approx. 0.44 hydroxyl equivalent) of 98.2% diethylene glycol monoglycidyl ether added. After post-reaction and work-up, a light brown product was crystalline at room temperature Epoxy resin with a content of 1.83 epoxy equivalents per kg received.

89 * 3 of the epoxy resin thus obtained were 15 »4 g Hexahydrophthalic anhydride heated to 80 ° C and mixed well. After heat treatment for 16 hours 100 ° C a hard molded material of high toughness and ivy resistance on glass was obtained.

109837/16 4Q

ORK31NAL INSPECTED

._ ₃₇ _ 1720Λ03

Example l4

225.0 g of polybutylene glycol with the average molecular weight 900 and with a hydroxyl equivalent weight of 450 were admixed with 87.0 (0.5 mol) of toluene-2,4-diisocyanate. The reaction mixture was initially kept under slight cooling, later by heating at 37 to 38 ° C until the isoeyanate equivalent weight of the mixture increases after approx. 45 minutes approached the calculated value of 624 (consumption half of all isocyanate groups). Then there was 81.0 g (0.5 hydroxyl equivalents) of the crude described above Butane-1,3-dol-monoglycidyl ether was added and left to react for 4 hours at 40 ° C and 5 hours at 50 ° C. then the isocyanate content could no longer be determined. Of the The epoxy content of the relatively low viscosity resin was 1.49 Epoxy equivalents / kg. It consists mainly of the compound of the formula

A ^Ä 4- Φ

CH ₂ -I

2 ⁶

■ · - ■ ^{σ H} 3 - <==? - NH-CO-O-

wherein Gv- freed the terminal hydroxyl groups Remainder of the polybutylene glycol. HO-G ^ -OH with the middle one Molecular weight of .9OO.

100 g of the epoxy resin thus obtained were heated to 80 ° C. with 133 S ^ 4-tetrahydrophthalic acid diglycidyl ester with an epoxy content of 6.4 epoxy equivalents / kg with 42.5 g of 3- (aminomethyl) -3,5,5-trimethyl-cyclohexylamine

1 O 9 β 3? / 1 6 4 O

well mixed. After a short vacuum treatment for removal the mixture was poured into preheated tensile body molds, and subjected to a heat treatment for 3 hours subjected at 90 ° C. The following were used on the traction bodies Properties measured:

Tensile strength according to VSM = 6.00 kg / mm ² elongation at break "" »5 % .

Example 15

To 200 g of chlorobenzene, 33.2 (0.25 mol) of 1,1,1-trimethylolpropane were added and 130.0 g (0.75 mol) of toluene-2,4-diisocyanate are added. The reaction mixture was initially through Cooling, later kept at 40 to 45 ° C by heating. After the isocyanate equivalent weight of the reaction mixture had risen to 452 (calculated value 486), 119 * 0 g were obtained (0.75 hydroxyl equivalent weight) diethylene glycol monoglycldyl ether (97.4%; hydroxyl equivalent weight 158.5; epoxy equivalent weight 163.0) and left to react for 1 hour at 40 ° C and 7 hours at 50 ° C. After the reaction has ended the cloudy reaction mixture was filtered through a pressure filter and finally brought to constant weight at 80 ° C./0.05 torr. It was a viscous epoxy resin with a

Content of 2.39 epoxy equivalents / kg obtained. It exists mainly from the compound of the formula

109839/1840

Ϊ7.20.Λ0

0 ^ fO-C ₂ E ^ -Q-00-mi

H ₉ C-CH CH

² \ /

NH-CO-OO ₂ H ₄ -OC ₂ H ₄ -O-OH ₂ -CH

62.8 g of the epoxy resin thus obtained were together with 133 g of diglycidyl hexahydrophthalate with an epoxide content of 6.4 epoxide equivalents / kg is heated to 50 ° C. and with 59 * 4 g of technical trimethylhexamethylenediamine [mixture of isomers from 2,2,4-trimethyl- and 2,4,4-trimethyl-hexamethylenediamine] well mixed. After a brief vacuum treatment to remove the air bubbles, the mixture was put into preheated tensile body molds poured and subjected to a heat treatment for 3 hours at 90 ° C. The following were used on the traction bodies Properties measured!

Tensile strength according to VSM elongation at break ""

5.00 kg / m ^ %

ORIGINAL INSPECTED

Claims (13)

Patent claims 1. Process for the production of new polyepoxides of the formula m-1 II -O-C-NH- CH, NH-CO — X- where η is an integer of at least 2, preferably 2 or 3, X is an oxygen or sulfur atom, R is an n-valent aliphatic radical which can be interrupted by oxygen atoms, sulfur atoms and carboxylic acid ester groups, and R _{1 is} an aliphatic radical with a terminal 1 , 2-epoxy group, which can be substituted by halogen atoms or interrupted by oxygen or sulfur atoms, but preferably a 2,3-epoxypropyl group, A is the radical of a glycol, a polyglycol, thiodiglycol or poly (thiodiglycol), of which the terminal hydroxyl groups have been removed, m = 1 or 2 and P = 1 or 2, preferably = 1, characterized in that a urethane pre-adduct of the general formula GH- O = C = K- I HH-CO-X- where η is an integer of Jn 2. preferably 2 or 3 »X is an oxygen or a sulfur atom, R is an n-valent aliphatic radical, which can be interrupted by oxygen atoms, sulfur atoms and carboxylic acid ester groups, 109837/1640 ORIGINAL INSPECTEP with a 1,2-epoxy alcohol of the formula converts, wherein R _{1 is} an aliphatic radical with a terminal 1,2-epoxy group, which can be substituted by halogen atoms or interrupted by oxygen or sulfur atoms, but is preferably a 2,3-epoxypropyl group, A is the radical of a glycol, a polyglycol, of thiodiglycol or of poly (thiodiglycol) from which the terminal i-hydroxyl groups have been removed, m = 1 or 2, and p = 1 or 2, preferably = 1, 2. The method according to claim 1, characterized in that that one starts from urethane pre-adducts based on polyethers. 3. The method according to claims 1 and 2, characterized in that that one starts from urethane pre-adducts based on polyglycols. 4. The method according to claim 1, characterized in that one starts from urethane pre-adducts based on polyester. 5. The method according to claims 1 and 4, thereby characterized in that urethane pre-adducts based on linear polyesters are used. 6. The method according to claims 1 to 5 *, characterized in that that glycidol is used as epoxy alcohol. 109837/18 ^ 0 -42- 1720/0 3 7. The method according to claims 1 to 5 *, characterized in that that the monoglyeidyl ether of a glycol or polyglycol is used as epoxy alcohol. 8. The method according to claim ¹ J, characterized in that the epoxy alcohol used is the technical monoglycidyl ether which contains a larger proportion of diglycidyl ether. 9. The method according to claims 7 b.is 8, characterized in that that the monoglycidyl ether of a glycol is used as epoxy alcohol. 10. The method according to claims 7 to 8, characterized in that that the monoglycidyl ether of a polyglycol is used as epoxy alcohol. 11. New polyepoxides of the formula 0 CH R ₁ y. JLi JLi —T- (OA -) - r-0-σ-ΝΗ— "CZ> 0 pl m-1 —r J ₁ NH-C-X- -Jn where η is an integer of at least 2, preferably 2 or 3 * X is an oxygen or sulfur atom, R is an n-valent aliphatic radical, which can be interrupted by oxygen atoms, sulfur atoms and carboxylic acid ester groups, and R, an aliphatic radical with a terminal -1,2-epoxy group, which can be substituted by halogen atoms or interrupted by oxygen or sulfur atoms, preferably but is a 2,3-epoxypropyl group, A is the remainder 109839/16 4 0 ORKaINAL INSPECTED -43 - f720403 Nes glycol, a polyglycol, thiodiglycol or poly (thiodiglycol) means, of which the terminal Hydroxyl groups have been removed, m = 1 or 2, and p = 1 or 2, preferably = 1. 12. An epoxy resin mixture from (1) the polyepoxide of the formula • ^ - ^ m-l, NH-C-X- η where η is an integer of at least 2, preferably 2 or 3 * X is an oxygen or sulfur atom, R is an n-valent aliphatic radical which can be interrupted by oxygen atoms, heavy felatome and carboxylic acid ester groups, and R _{1 is} an aliphatic radical with a terminal 1,2-epoxy group, which can be substituted by halogen atoms or interrupted by oxygen or sulfur atoms, but is preferably a 2,3-epoxypropyl group, A denotes the radical of a glycol, a polyglycol, thiodiglycol or poly (thiodiglycol), from which the terminal hydroxyl groups have been removed, m = 1 or 2, and P = 1 or 2, preferably = 1 and (2) the diglycidyl ether of a glycol or polyglycol. 13. Curable mixture of (1) the polyepoxide of the formula 0 CH 11 Ρ ^ ₁₁ -OC-NH-O 0 NH-C-X- -in 9837/1640 where η is an integer of at least 2, preferably 2 or 3, X an oxygen or sulfur atom, R an n-valent aliphatic radical »which can be interrupted by oxygen atoms» sulfur atoms and carboxylic acid ester groups, and R, an aliphatic radical with a terminal 1,2-epoxy group which is substituted by halogen atoms or by oxygen or Sulfur atoms can be interrupted, but is preferably a 2,3-epoxypropyl group, A is the remainder of a glycol, of a polyglycol, thiodiglycol or poly (thiodiglycol) of which the terminal hydroxyl groups have been removed, times or 2 1st, and p »1 or 2, preferably ■ 1, (2) a hardener for epoxy resins, and optionally (3) the diglycidyl ether of a glycol or polyglycol or * »!». 109832/1640