DE1545061A1 - Curable preparation - Google Patents

Description

dr. w. Schalk dipl-ing. Peter Wirth

DI PL.-! NG. G. E. M. DAN N EN BERG DR. V. SCHMl ED-KOWARZI K

._ Union Carbide _ .. Corporation

270, Park Avenue

New York 17th N.Y. /UNITED STATES

The present invention relates to curable, polymerizable preparations consisting of a polyepoxide which at least one to two adjacent cycloaliphatic carbon Atoms contains bonded oxirane oxygen atom, a polycarboxylic acid compound and a monomeric, ethylenically unsaturated compound, the polyepoxide and / or the acid compound have at least one ethylenic double bond, must ... The present invention further relates to fusible chemical-releasing intermediates and to those by curing of the above curable polymerizable preparations obtained hardened, polyamide products.

The polymerizable preparations according to the invention can easily used in resin forming processes such as enrobing, coating, bonding, molding, pouring, pouring over and embedding will. These polymeric preparations can be solid Materials such as fillers and pigments to achieve

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different effects / their physical properties and color. With or without such added solid materials, the polymerizable preparations can produce small recesses of. Fill in forms. The polymerizable preparations can be cured in molds with intricately shaped surfaces, and the resulting molded resins show the precise and fine details of the shape. The polymerizable preparations can also be used with advantage for heating fragile objects, such as electronic components. In addition, the polymerizable preparations according to the invention can be easily hardened to form bubble-free resins.

The polymerizable preparations according to the invention and The prepared preparations have various highly desirable and unexpected benefits. The use of the monomeric, Äöjrlenisch unsaturated compound in the curable system is reduced die Schninelzte: .. ^ erature very essential and prevents the Viscosity of the curable system compared to the corresponding curable systems without the unsaturated compound. It is noted that the low-melting preparations as opposed to the short epoxy formulations used, for example, for molding represent a decisive advantage. Generally increased the incorporation of the monomeric, ethylenically unsaturated compound the reactivity of the hardenable system is noticeable, whereby a gelation at much lower temperatures, e.g. room temperature, in a shorter time than with corresponding systems without the monomeric, ethylenically unsaturated compound

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^::; -i ORIGINAL

can be effected. Rapid gelation times, especially at relatively low temperatures, offer a significant advantage in the mass production of plastic parts, since the deformation system is only used for a minimum time. Many of the hardened resins according to the invention show an unusually high heat resistance at elevated temperatures, due to the monomeric, ethylenically unsaturated organic compound contained in the hardenable material. In general, the hardened resins according to the invention have eixie compared to corresponding hardened resins which have been produced from hardenable preparations without the iltilylenisch compound. significantly improved resistance to water and corrosive substances. ■ e: -, ij.r;: in reduced the use of the complain, llth / le-.iacn :. ·> . e -A: _: activated connection the costs of the erf L ndu: i yes according to: -är'tiiur-. · /. Preparations are considerably compared to one another. The same weighting applies: the curable preparations without the ethylenic compound. This reduction in price was made possible by reducing the amount of the most expensive component, ie the epoxidized .. Polyi-.ei'isates, indei; e3 is replaced by the relatively cheap at. ylenic component. Veiterhix: enables the process according to the invention: the production of resins for very special purposes, since the concentration of the components in the preparation varies individually. So :: ■. & :. For example, the carboxyl concentration in the hardenable: preparation with constant: keeping the epoxy concentration constant eri: oheü.

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According to the invention, the heat-set, hardened resin, e vary from soft and "pliable to hard and firm products, depending on the ratio, functionality and chain * length of the components used. These resins are insoluble in many organic solvents. The hard, infusible ones Solid, thermoset resins can be processed into desired shapes and configurations and used to achieve polished to a pleasant appearance.

The inventive curable polymerisierbareiPräparate consist AU3 (a) a ¹ polyepoxide, the off at least one bound to adjacent cycloaliphatic carbon atoms Oxiransauerst atom, (b) eiiier polycarboxylic & ureverbindung and (c) a monomeric ethylenically unsaturated compound other than the polynierisierbaren ethylenic groups does not contain any functional groups that are reactive with adjacent epoxy groups and carboxyl groups, with the prerequisite that in addition to the monomeric, ethylenically unsaturated compound, at least one component contains at least one ethylenic group that is polymerizable with the monomeric, ethylenically unsaturated compound, in relative terms Uengen that there are 0.16-5.0 carboxyl groups of the acid compound per epoxy group of the polyepoxide and 0.002-5.0 ethylenic groups of the monomeric, ethylenically unsaturated compound per ethylenic group of the other components.

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The present invention further relates to a resin-forming process, daa characterized in that at least (a) one polyepoxide, the at least one to adjacent cycloaliphatic carbon atoms bonded oxirana oxygen atom contains, (b) a polycarboxylic acid compound and (c) a monomeric, ethylenically unsaturated compound, which except the polymerizable ethylenic group does not have any functional groups with adjacent epoxy groups and carboxyl groups are capable of reacting, with the proviso that besides of the monomeric, ethylenically unsaturated compound, at least one of the components to be reacted is at least one ethylenic agent Contains group which is polymerizable with the monomeric, ethylenically unsaturated compound, in the presence of a catalyst is reacted with free radicals at a temperature between 15-275 ° for so long that a hard, solid resin is obtained is, with such relative amounts being used that '0.16-5, .O carboxyl groups of the acid compound per epoxy group of the polyepoxide and 0.002-5 »0 ethylene groups of the monomeric) ethylenically unsaturated compound per ethylenic group of the other components.

It is advisable that the - '4e-ft relative proportions of polyepoxide, ethylenically unsaturated Polycarboxylic acid and monomeric, ethylenically unsaturated compound are such that 0.16-5.0 carboxyl groups, -COOH, of the acid compound are present per epoxy group dea polyepoxyda. The amount of the monomeric, ethylenically unsaturated compound is most appropriately based on the ratio of the ethylenic

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Groups of the monomeric, ethylenically unsaturated compound per ethylenic group in the acid compound and / or the polyepoxide is included, based. It is therefore advisable to to use the monomeric, ethylenically unsaturated compound in such an amount that 0.002-5.0 ethylenic groups of the monomeric, ethylenically unsaturated compound per ethylenic Group of the polyepoxide and the polycarboxylic acid compound are present. The polycarboxylic acid compound is useful a polycarboxylic anhydride, but it can also be a polycarboxylic acid or a mixture of polycarboxylic acids and acid anhydrides are used. The expression "Ethylenic group" refers to the / C = C ^ group. In the case of an acid anhydride means the expression "carboxyl groups of the · polycarboxylic acid compound" the carboxyl groups that would be contained in the corresponding polycarboxylic acid. Maleic anhydride, for example no carboxyl groups per se; however, the corresponding polycarboxylic acid is maleic acid, the two free carboxyl groups own. So has according to the above imprint Maleic anhydride has two carboxyl groups. In other words: the expression "carboxyl groups of the polycarboxylic acid anhydride" means those contained in the hydrated polycarboxylic acid anhydride Carboxyl groups. There are / relative proportions of polyepoxide, ethylenically unsactivated polycarboxylic acid compound and monomeric, ethylenically unsaturated compound, so that 0.33-4.0 carboxyl groups of the acid compound per epoxy group dee polyepoxides and 0.2-2.0 ethylene groups of the monomeric, ethylenically unsaturated compound per äthylenigchei Group of the polyepoxide and the acid compound are present.

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Sometimes it is square in the curable preparation To incorporate polyol in an amount such that up to 2.0 hydroxyl groups of the polyol per epoxy group of the epoxy are present are. When calculating the amount of the monomeric, ethylenically unsaturated compound to be used in the presence of a polyol in the preparation is that optionally present in the polyol Ethylenic groups are added to those in the polyepoxide and the acid compound. Preferably 0.16-2.0 are hydroxyl groups of the polyol per epoxy group of the epoxy present.

Some of the curable preparations according to the invention or completely hardened, inde: .. the temperature in the Range from 15 ° or less to 275 ° or more, preferably between 25-200 °. A higher curing temperature provides a thermosetting or thermosetting Resin in less time than a lower curing temperature. A useful procedure is e3, the hardenable preparations first to be heated to a temperature between 25-150 ° for partial hardening. A Temperature of 100-225 ° can be applied. However, any one or a combination of these can be used to achieve full cure or two or more temperatures in the above range of 15-275 ° can be applied. In casting processes, the preferred minimum temperature is the normally solid curable preparation the one in which the preparations form a uniform melt, while for coating and for the production of laminates the use of solvents lower temperatures enables.

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The time to achieve partial or full curing is determined to a certain extent by factors such as the particular component used, the proportions of the components used, the use of a catalyst and the curing temperature. In general, the time to achieve complete hardening can vary from a few minutes to 24 hours, for example from 10 minutes to 20 hours, which depends on the mutual relationship between the above factors.

If necessary, acidic or basic catalysts can be incorporated into the curable preparations according to the invention in order to increase the reaction rate of the polycarboxylic acid compound and the polyepoxide. In general, it is appropriate to use a catalyst to a zr. aiilouueu. iO-100 content to be added to the curable preparation. Before, w; In addition, after the catalyst has been absorbed, it is advisable to stir the hardenable preparation in order to achieve a homogeneous mixture. If necessary, higher temperatures can also be used, but there is the possibility of premature and localized hardening around the catalyst particles before the formation of a homogeneous, hardenable mixture. In most cases it is important to achieve a homogeneous mixture before the initiation of substantial hardening; low Kishte ^ leratures of the order of magnitude given above are used. Kaxalysatcrkonzentration and Hardening temperature _x temperature influence the hardening rate, whereby

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higher concentrations and temperatures result in faster curing effect than lower. The catalyst concentrations can be varied over a wide range and based on the desired curing speed and the one to be used Curing temperature can be selected. It has been found that catalyst concentrations of 0.001 or less bl3 5 or more% by weight, based on the weight of the polyepoxide component, in the production of valuable thermosetting resins from the curable preparations are advantageous.

Basic and acidic catalysts that can be used in the curable preparations are, for example, the metal halide Lewis acids, v / iü boron trifluoride ⁴ Id, aluminum chloride, zinc chloride, stannous chloride, ferric chloride, boron trifluoride-piperidine complex, the boron trifluoride-1,6-hexanediamine complex, the boron trifluoride monoethylamine complex, the boron trifluoride dimethyl ether complex, the boron trifluoride diethyl ether complex and the boron trifluoride dipropyl ether complex; the strong mineral acids such as sulfuric acid, phosphoric acid, polyphosphoric acid and perchloric acid; the saturated aliphatic hydrocarbon sulfonic acids and the aromatic hydrocarbon sulfonic acid, such as, for example, ethyl sulfonic acid, propyl sulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mayhalic sulfonic acid and low-alkyl-substituted benzenesulfonic acid; the alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; the amines, such as ego ^ -Methylbenzyldimethylauiin, dimethylethylamine, triethylamine, tripropylamine and trimethylammonium hydroxide. If the catalyst and the curable preparations are miscible, the catalyst can also be added as a solution in an inert, normally liquid, organic medium. Typical media for the catalyst include the

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organic ethers, such as' Diethyl ether and dipropyl ether; the organic esters, v / ie e.g. ethyl acetate, ethyl acetate, Methyl propionate and ethyl propionate; the organic ketones, such as acetone, cyclohexanone and methylcyclohexanone.

Furthermore, it is often expedient to use a free radical-forming agent such as z.3. Peroxide catalysts, for easier polymerization of the monon.eren, ethylenically unsaturated compound with the unsaturated components, ie polyepoxide, poly-carboxylic acid anhydride and any polyol present, to be added. It is preferred to add the free radical-forming agent to the curable-i system immediately before curing; Such agents which form free radicals are, for example, benzoyl peroxide, ethyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, pl.Ient_anhydrop3roxyd, tert.-butylnydroperoxide, cumolnydroperoxide, acetylperoxide, acetylperoxide and tert-butyl peroxide, lauro-butyl peroxide, lauro-butylperoxide, cyclohexanone-butzo-benzo. Can llitteln lift forming the free Eadikale yet certain metallic Aktivierun _e 3-medium in the curable systems incorporated v / ground. Such activating agents are, for example, the salts of cobalt, copper, manganese, calcium, zinc, lead and iron, such as, for example, 3. Cobalt naphtenate, cobalt octanoate, and lead octanoate. The concentration of the free radical forming agents and the activating agents can be in the range from 0.001 or less to 5 or more% by weight, based on the total weight of the components in the curable preparation.

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The appropriate as a component in the erfindun ^ sgeiaaßen preparations Polye _x oxide are monomeric Lloleküle XAIT an accurate KoIelculargewicht. These polyepoxides contain at least one Qx bonded to two adjacent cycloaliphatic carbon atoms as an acidic atom, ie at least one adjacent epoxy group ι / C-Cy, the carbon atom of which is part of a

Form cycloaliphatic hydrocarbon nucleus. The cycloaliphatic nucleus expediently contains 5-7 carbon atoms, including the jipoxy carbon atoms. Saturated polyepoxides in which all oxirane oxygen atoms are bonded to neighboring cycloaliphatic carbon dioxide are preferred. It goes without saying that only one oxirane oxygen can be bound to any pair of adjacent or adjacent carbon atoms. The term "saturated polyepoxides" relates to polyvU _x CXyds which are free of ethylenically unsaturated bonds, ie / C = Cv, and acetyleiiiscl: unsaturated bonds, ie, -C = C-. Saturated Iiai-> oxyde _f whose ueide Oxiranaauerstoffatome linked to cycloaliphatic carbon atoms, :,'ll preferable instesondere polyepoxides containing only carbon, What a contained eratoff- and oxygen atoms.

(next to de.; Oxira..sauer3toff)

The acid off at oae / j. Can see p. are present with essential oxygen, e.g., C-O-C; Oxygen ii ;. an ester group, e.g.

ti

ο - ^c - ° -

I!

and oxygen in a carbonyl group, e.g., -C-. In the invention With new preparations, only one polyepoxide or a mixture of two or more polyepoxides can be used.

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Suitable polyepoxides are, for example, the alkanediol bis (3, 4-epoxycyclohexanecarboxylates), the alkenediol bis- ^ H ^ epo-xyc, / ⁰ ! ⁰ -hexaiicarb oxy late), the alkazid iol-bis-

iert-3, 4-epoxycycloiiexancarboxylate), the oxaalkanediol-bιοί low-alx _i .ylöub3tituierten-3,4-epoxycyclohexanecarboxylate), the alkanetriol-tris- (3 »4-epoxycyclohexanecarbox _< ylate), the AlKcntriol <ylate 4-ei.oxycyclohexanecarboxylates), the alkanetriol tris- (lower-alkylsubs "fcit'.iierten - 3, 4-epoxycyclohexanecarboxylates) / and the oxaalkanetrioi-tris- (lower-alkyl-substituted i-3,4-epoxycyclohexanecarboxylates). The above polyol-. poly- (3 _} 4-epoxycyclohexa ^ carboxylate) 'can be prepared by entax.rechei.den polyol-pol / - (cyclohexenecarboxylate) with at least e "^ er 3tüohio: rietri.jcj: en." close e PereüSiguL- iure (preferably as Löjung in ethyl acetate) at a temperature between 25-90 ° is epoxidized so long that the oxirana oxygen a.-i de: i places of all contained in the polyol-poly-cyclohexenecarboxylate) Carbon-carbon double bonds are introduced. The polyol-poly-cyclohexene carboxylates, for their part, come from known condensation processes, e.g. ju. Esterification of a polyol, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1, ^ - propylene glycol, 1,3-propylene glycol, the polyoxyethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1, D-hexanediol, the octanediols , the octadecanediols, the butenediols, the pentendicle, the witch's idiols, the octenediols, 1, 2, '3-prcpantriol, tri: .. et..ylolmethan, 1,1,1 -trimethyloläthan, 1, 1, i -Triir-ethyloxropan, 1,2,6-hexanetriol, cycloalipLatiache iriols and aronatisciie triols; , r.it a 3-Cyclohexencarbon- ■ /, the

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Acid, such as 3-cyclohexenecarboxylic acid and lower alkyl-substituted ones 3-cyclohexenecarboxylic acid, the Au3t used here The phrase "lower alkyl substituted" refers to an alkyl radical with 1-4 carbon atoms.

Other suitable polyepoxides are, for example, the bis (3> 4-epoxycyclohexylniethyl) hydrocarbons, the arboxy late and the low alkyl-substituted bis (3 »4-epoxycyclohexylmethyl) hydrocarbon dicarboxylates, such as bis (3f4-epoxycyclohexyluethyl) - oxalate, bio- (514-epoxycyclohexylethyl) malonate, bis- (3,4-epoxy-cycloliexylmethyl) -sucinate, bis- (3,4-epoxycyclohexylinethyl) -glutarate, bis- (3,4-epoxycyclohexylethyl) adipate, Biü - (3,4-epoxycyclohexylniethyl) maleate, bis (3,4-epoxycyclohei.yli :: ethyl) tetrahydrophthalate, »bis (3,4-eiJOxyGyclohexylmethyIl) -oitraconate, bis- (3» 4-epoxyoyolohexyln: ethyl) -iaocitraconat, bis (3, + -epoxy-ö-methylcyclohexyLi-ethyl) -fu-marat, bis (3,4-e _x j0xy- oyclohex _l / liiiethyl) pimelate, bis (3 »4 epoxyoyclohexy! methyl) terephthalate, bis (3> 4-epoxyoyclohexy! methyl) azelate, bis (3> 4-epoxycyclohexylmethyl) sebacate, bis (3 »4-epoxyoyolohexylitethyl) itdüonate, bio- (3 »4-epoxycyolohexylmethyl) -hexahydrophthalate, Bia- (3'j 4-epoxycji clohexylmetliyl) -phthala t, bis (3> 4-epoxycyclohex / liiiethyl) glutaconate and bis (3,4-epoxycyclohexylmetliyl) - / ijdromuconate ,,

Other suitable polyepoxides are the monoesters of 3 »4-epoxycyclohexylmethanols and 3 »4-epoxycyclohexanecarboxylic acids, such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxy-Iab , I -methyl-3 »4-epoxycyclohexylmethyl-i -metliyl-3,4-epoxycycloauxan carboxylate, 6-methyl-3 ^ -epoxycyclohexyliiiethyl-o-methyl-

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3 ^ -epoxycyclohexanecarboxylate, 2-'Ath ₀ 1-3, 4-epoxyuyclohexylmethyl-2-ethyl-3 ^ -epoxycyclohexanecarboxylate, 4-n-propyl-3,4-epoxyoyclohexyli;: ethyl-4-n-propyl- 3 »4-epoxycyclohexane carboxylate, 5-l3obutyl-3,4-epoxycyclohexyl: i-othyl-5-i3obutyl-3,4-epoxycyclohexane carboxylate, 3,4-low alkyluuostituiertes Epoxycyclonexyl: aetiiyl-niedrigalkylsub3titaierte3-3,4-epoxycyclohexancarboxylafc, halogensubatituiertea y , 4-.Epoxycyclon ^ XYL · ..ethyl-ll.i, lie; Jubstituierte3-3,4-ei _r ■ oxycyclohäxancarboxylaΐ, l-Ciilor-3, 4-EJ, oxyoyclohexyliuethyl-i ^ -chlort -epoxycycloruixancarbuxylat and 2- lirou.- p, 4-epoxycyclohexylm8tiiyl-2-bromo-3, 4-epoxy cyclohexyl bicarboxylate. Other suitable polyepoxides are the ^ -oxatetracyolo- / 4.4.0.1 '.0 "' y-undec-e-yl-vicinal-epoxyal ^ yl ethers, the 3-oxatetracyclo- / 4Γ.4.0.1 ' .O ^df ' y -uaaac-Q-jl-v ± oe _v cxj oycloalkyläther, the 3-0xatetracyclo- / i ".4.0.1 " .0 'y-undec-S-yl-vic-epoxycycloalxiylalkyläther, the 3-Oxate tracyclo- / ΐ. 4.0. I ^{7 '10} .C ² ' fZ-uadeo-S-yl- '^ - oxytr ic / clo- ^ J. 2.1. 0 ² 't / oct-6-yl ether and the 3-0xatetracyolo- _(/4".4.0.1 ^{7' 1R} .C ^ '^ 7-undec-8-yl-p-oxatricyclo-ZJ.2.1 .0 '^ / - oct-ö-ylalkyläither, especially 3-0xatetracyclo- / 4.4.Gl' .0 ' l7 - an.dec-ü-jl-2,' 5-e £, oxjx) TOüjl äther, 3 -0xatetracyclo- _/ /4.4.C. 1 '.0 ^ y-VLiAao-t-ji-jf ^ -e ^ oy ^ - butyl ether, 3-Oxatetraoyclo - /. 4 ~ · 4.0.1 ^{7> 10} .ü ² '^ 7-undec-8-yl-2,3-epoxybutyl ether, J5-oxatetracyclo- / 4 ^ 4.Ü.1' .0 '37 -undec-L- ^ 1-3,4-epoxyliexylether, 3-0xatetracycloG - / J "» 4.0.1 '.0'"' yu.aa.ec- 8-yl-5,6-epoxyhexylätiier, 3-0xatetracyclo-Z4" .4.0.1 ⁷ ' ¹⁰ .0 "» V- * undec-8-yl-7,8-epoxyoctyl ether, 3-oxatetracyclo- ^ T.4.0.1 ⁷ '. & \ -undec-e-yl ^ -methyl- ^, 3-epoxypropyl ether, 3-oxatetracyclo- / J. 4.0.1 ^{7 "Ί} ° .O ² 't7-undec-8-yl-2-ethyl ~ 2,3-epoxyhexyläther, 3-Oxatetracyclo-Zi" .4.0.1 ⁷ * ¹ °. O ² * tZ-undec-8-yl-9.1 C-epoxystear / lr

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ether, 3-oxatetracyclo- / 4.4. ü. 1 '' ¹ ° .O ^ »^ - uiidec-S-yl-g, 10,12,13-diepoxystearylether, 3-0xat etracyclo- ^. 4 .Ü.1 ' ' .0 '^ / "- undec-8-yl-2, 3-epoxyeyclopentyl ether, 3-oxatetracyclo-, / 4.4.0,1". O ^ undeo-8-yl-2 , ^ - epoxycyclüpentyl: .ietiiylätLer, 3-0xytetracyolo- / 4.4.OI '.0' Jy ^ -u.idec-S-yl-alkylaubatituiert-i ^ -epoxycyclohexyläther, 3-0xatetracyclo- / 4 ".4.0.1 ^{7 > 10} .Ü ^2> ^ 7-uiidec-8-yl-3, 4-epoxycycloliexylt.Uiier, 3-0xatetrac, / clo- / 4 ".4.ü.1 '* .0' _y-undec-6- yl-2, '5-epoxycyoloiiexyi: t.-er, ij-0xatetracyclo- / 4 ~ .4.0.1 * .0 * y uiide3-fc-y 1-3,4-ei-oxycycloa-exylr.etiiylätiier, 3 -Oxatetracyclo-, ^ / 4 ".4.0.I" .0 ^ ' y-vivAec-S-yl-o-zietliyl-JfA-eDOXjOjclohexiyl inetiiylather, 3-0xnte «r, c, clc- / 4.4.0.1 ⁷ . ' ^1Ü . O ^ 'f / -u :: dec-i-yl-5.-r.iethyl-3 i4-epcxyoycloiiö ^ yl; -ci; L _{t /} -lätIier,' j-Oxatetracyclc ^ /4~T4.C. 1 '.0 * "* ^ 7 ~ undec-8-yl-u- ylaubstiuaier -3-oxatricyclo- / 3.2.1.0 ² ' ^ 7-oct-ö-ylLther and 3-Oxatetracyolo-ZT · 4.0.1 ⁷ ' ¹ °. 0 ^k * ' ¹ J uiadec-S-yl-i-oxatriu ^ elo- ^ i. Jl .0'"'_ / - oct ~ 6- / l-üther ·

Other suitable polyepoxides are a.t, the bis- (vicepoxycycloalkyl) -aulfOiie, the Ms- (vic-epox / cycloalkylalkyl) -3ulfones and the Vio-iiioxyalkyl-3-oxatetracyclo- / T ".4.0.1" .0 '_ / undec-8-yl-3ulfone. E3 it is pointed out that the obigeii "Diepoxysulfonen the Vic-epoxy ^ rappe through, a Κοη1βη3ΐο1ΐ-atom from the sulfon group is removed. Such Biepox ^ sulfones are 3.F, BiS - (^ f? -ei'Oxyayclcpe: -t;} l) - sul ± Oii, Bia- (lower alkyl-substituted - ^, 3-e ^ axyc, yelepuntyl) - Bulfon, Bis- (2-ethyl-2,3-epoxycyclope :: tyl) sulf cn,? iu- (4-R-butyl -.;, 3-epoxycyclop6nty] 3 sulfone, bis- (3,4-epoxycyclohexyl) -3ulfone, Bi3- (lower-alkyl-substituted-3,4-epoxycyclohexyl) -uulxone, 5i3- (2-niethyl-3,4-epoxycyclohexyl) sulfone, 5ia- (5-ieopropyl-3,4-epoxycyclohexyl) -

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sulfone, bis- (3i4-epoxycycloheptyl) -sulfone, Bi3- (lower-alkyl buttituated-3 _f 4-epoxycycloheptyl) -sulfone, bis- (2,3-epoxycyolo-, pentylalkyl) -sulfone, bis- (2,3- epoxycyclopentylmethyI) sulfone, Bi3- (2,3-epoxycycloperitylpropyl) sulfone, bis- (3 _f 4-epoxycyclohexylalkyl) sulfone, ice- (3 »4-epoxycyclohexyliie-fch $ l) -3ulfone, bis- (3, 4-epoxycyclohexylbutyl) sulfone, bis (3 ₁ 4-epoxycycloheptylalkyl) -3ulfone, bis (3f4-ei? Oxycycloheptylmetnyl) sulfone, Bi3- (3 "xajfctricyclo- / J.2" .1 .O ^ 'j ^ -oct-e-yli-sulfon, Bia- (3-oxatetracyclo / 4 ".4.Ü.1 ^{7> 1} ° .0 ^{2> 4} / - ^ ndec-8-yl) -aulfon, 2,3- Epoxypropyl-2,3-epoxycyclopentylsulphone, 2-methyl-2,3-epoxypropyl-2 ^ -epoxycyclopentylEie fchyloulf on, 1C, 11 -Epoxyoctadecyl-3> 4-epoxycyclohexylsulphone, 2-diethyl-2,3-epoxyhexyl-3-oxatricyclo - / 3.2.1.0 'y-oct-6-yl-sulfone, 2,3-epoxycyclopentyl-3-oxatetracyclo- / J ".4.0.1" »^ .O' ^ 'fZ-'u.ndec-B -yl-sulfone, 2-methyl-3,4-epoxycycloliexyi - ^^ - c ^ u ^^ yclopentylethylsulfone and 3 »4-epoxypentyl-2-n-butyl-3f 4-epoxy cyclohexylsulfone.

Other suitable polyoxides are, for example, bis (vic-epoxyayclohexoxyalkyl) sulfone, Bis- (lower-alkyl-substituted-vicepoxycyoloiuxoxyall.yl) -sulfone, Bis-Cvic-epoxycyclohexylalkoxyalkyl) -3Ulfon, Bia-C-lower alkyl-substituted ^ -oxatricyclo-.2.1.0 'y-6-octoxyalyl) sulfone, bis- (3-oxatetracyclo-.4.O. Ί '' .0 * '^ 7-6-uride c oxy alkyl) -sulf on, Vic-epoxyalkoxy-

^ -oxatricyclo / J.2.1.0 'fT - ^ - octoxyalkylsulphone, and Vic-epoxycyclohexoxyalkyl-: 5-oxatetracyclo- / 4.4.0.1' * .0 'V-8-undecoxyalkylsulfori. Specific examples of the above diepoxy diet sulfones are %. B. bis- (3,4-epoxycyclopropyl) -3ulfone, bis- (2-diethyl-'3,4-epoxycyclohexoxyätriyl) -ulfone, Ei3- (2,5-di: r.ethyl-3,4-epox / cycloiiexoxypropyl) -sulx on, 3ia- (2, 3-epoxy-

009813 / 16U

cyclohexylmethoxyethyl) -ou.lfon, bis- (3,4 - epoxjroyclohexylätlioxy-

propyl) sulfone, bis (lower alkyl-substituted-3,4-epoxycyclonexylmethoxypropyl) sulfone, bis (3> oxatriGyclo- / 5.2.1.0 'y-6-octoxyethyl) -3ulfone, bis ~ (3-oxatetracyclo / 4.4.0.1 ''.0'y-8-undecoxyprppyl) -sulfone, 2 ^ -Epoxypropoxyäthyl ^ -oxatrioyolo- / 3.2.1 .0 * 37-6-OGtOXyPrOPyIsUlI ¹ On, 2-Ätliyl-2,3-epoxyhexoxypropyl-3,4 -epoxycycloh.exoxyäthylsulfon, g, 10-Epoxyoctadecoxypropyl-2-Metii, yl-3,4-epoxyGyclohexoxyät] aylsulfon, Bis- (ethyl-substituted-3-oxatetraoyclo- / 4 ".4.0.i '^{7> 10} .0 ² ' i7-8-undecoxyethyl) 18 sulfone, bia- (dimethyl-3Ub3tituiert-3-oxatetraoyclo-i ^. 4.0.1 ⁷ ' ¹ ° .O ² ' f / -8-undeoojtyethyl) sulfone and Bi3- (lower alkyl substituted- 3-oxatetr ^ cyolo- /? ". 4.0.1 ⁷ ' ^Ί °. O ² » ^ / - Si ^ decoxyethyl) sulfon.

Further polyepoxides are <j »U ¹ sulfonyldialkyl bis (vicepoxycycloalkanecarboxylate), u, u ^! -Sulfonyldialkyl-bi3- (vicepoi / cycloalkylalkanoate) and Cj, c *) '- sulfonyldialkyl-bia- (3-oxatricyclo- / 3.2.1.O'lZ-octane-o-carboxylate). The poxydiester sulfones of the above type are, for example, 2,2 ^r- sulfonyl diethyl bis (2,3-ei-Oji / cyclopentanoarboxylate), 4,4'-sulfonyldibutyl bis (3 »4-epoxycycloiiexancarboxylate), 3» 3 ^t - Sulfonyl dipropyl bis (3> 4-epoxyoyoloxieptane carboxylate), 2,2'-sulfonyl diethyl bis (2,3-epoxycyclopentyl acetate), 4,4'-sulfonyldibutyl bis (2 ^ - ^ poxyoyclopentyl propionate) and 2.2 '-Sulfonyl diethyl-bi3- (3-oxatricyclo-.2.1.0 ² ♦ IZ-oö tan-6-car / boxylat).

BATH ORIGINAL

OO9813 / 16U

V / urther Polye> oxyde aind example, the 3-OxafceOracyclo-4.OI ⁷ '.O ^2' ^ undec-b-yl-vic-epoxyalkanoate that 3-0xatetraoyclo- / 4.4.0.1 ^'Ü .O' y -undec-8-yl-vic-epoxycycloalkanecarboxylates, the 3-oxatetracyclo- / 4.4.0.1 ⁷ ' ^1Ü .O ² ' J7-undec-B-ylvis-epoxycycloalkylalitanoate and the 3-oxatetracyclo-

6-al ^ canoate, especially 3-0xatetracyclo- / 4.4.Ü. I "" .0 ^ 'yundec-8-yl-2,3-epoxypropionate, 3-0xatetracyclo- / 4.4.0.1' .0 ^ ' undec-S-yl-2,3-epoxybutyrate, 3-0xatetracyolo- / 4.4.0.1 '.0 ' J undec-8-yl-9,10-epoxystearate, 3-0xatetracyclo-Z4_.4.0.1 ⁷ ' ^l0 .Ü ^ ¹ ^ undecI-8-yl-9, 10.1 2, 13-diepoxyotearate, "J-Oxatetracyclo- ^ 4.4.0.1" .0 'y- \ xndeG-ü-jl-2,3-e ioxycyclopentanaarcoxylat, 3-0xatetracyclo- / 4.4.ü.1' .0 ^ 'V ~ ^{un (} iec-8-yl-3, 4-e ^ oxycyolopenisane carboxylate, 3-oxate e tr acy clo- / 4 »4-0.1 '.0 ' Vu.ndec-E: -yl 4-methyl-2 ^ - epuxycyclopeuöancarboxylat, 3-Oxatetracyclo- ^ 4.4.0.1 '.0'y-uridec-S-yl-2,3-epoxycyclG'iexarxcarcoxyl: it, 3-0xatetracyclo-, / 4.4.0.1 ⁷ * ^1C . O ² » ^i] J-mLäac-Z-jl-2-z.3tYij 1-3, 4-e ^ oxycycloh.exancarboxj'lat, 3-0xatetracyclo- / 4.4.0.1 ' ^υ .0 ^ ^lj ''_ / - undec-b— yl-3-oxatricyclo - / '3.2.1 .0' y-octano-carboxylate and 3-oxatebracyclo- / 4.4.0.I ⁷ ' ^] ° .O ² '! / -

Other suitable polyepoxides are, for example, 4-VinyloyGlohexendioxyd, Dicyclopsntadie.ilioxyd, .Bis- (2,3-e ^ oxycyclop ^ ntyl) -ether and bis- (3-oxatetracyclo- / 4.4.0.1 ^{7> 1Ü} ..0 ^{2> z} i7-undec-8-yl) - "fclther. The diathermic epoxides described in US Pat. No. 2,543,441 are also inventive; suitable.

009813 / 16U

The diepoxydiestersulfones are known to be produced, inde,.> E.g. iV, V '-Tliioalkanol-bis-icycloalkenecarboxylate), ^ ₁ 6 </' ^! - Thioalkanol-ols-Cbicycloalkenylcarboxylat) is reacted with at least 4 KoI peracetic acid per lüol sulfide reactants under the reaction conditions shown below. In this reaction, the sulphide part, ie -S-, becomes the sulphonyl group, i.e.: i. -Su ^ -> oxidized and oxirane oxygen in the place of the two charcoal, is of f-charcoal ^ is introduced off -double bonds of the sulfide. The tv ¹ » U '-thiodialkanol-di-Cunsaturated-ester) in turn can be prepared by diesterification of stochiOL.etrische.il liengen of a thiodialiranol, such as thiodi _c : lycol, 3 | 3'-thiodipropaiiol and 0,8-thiodioctanoi , with eJ, er unsaturated organic acid, such as 3-Cyclonexen-? .- ir,,:. oäure and bicyclo- / 2.2.1 _J 7-5-heρten-2-carboxylic acid in Iclaol -l-rr other ^. eacsprecLe-iden inert organic ^ operating under V'-r \ e; .dung a sulfuric acid catalyst and inde :: i so lan _£ ~ e i: u ;; Reflux is heated until the water formed by the Bea-Ltion completely irit as the lower part of the distillate. Then the catalyst is mixed with a. Neutralized excess of acetate; after filtering, the esterification product is distilled and the corresponding i-delv, ί-v'-thiodialcar-ol, di-cyclo-saturated ester) is produced.

The Diepoxydiäthersulfone can be prepared as follows: for example Mvinylsulfon is with a Gycloiiexenol or Polycyclohexencl at high leuveratures, e.g. 50-100 °, in the presence of a basic catalyst for the production of the corresponding Kono or Diether sulfone (which depends on the concentration of the Eeaktion participants) to ₆ it sets. How to deliver *

009813 / 16U

- ■ 20 - ■ 15A5061

e.g. less than 2 moles of ethylenic unsaturated alcohol (ROH)

per Iviol Divinyloulfon according to the following equation, the diethersuli'on:

2 ROH + (CH ₂ = CH) ₂ SO ₂ - ^ RO-CHgCHgSO ₂ CHgCHg-OR

The use of less than 1 mole of ethylenically unsaturated Alcohol (ROH) per mole of divinyl sulfone provides the monoether sulfone as follows:

ROH + (CH ₂ = CH) ₂ SO ₂ -> RO-CH ₂ CH ₂ SO ₂ Cli-CH ₂

The monoether sulfone product obtained can then be reacted with a molar overshoe of another non-saturated alcohol (R ¹ OH) to produce an unsymmetrical dietersulfone as follows:

It ¹ OH + RO-CH ₂ Ch ₂ SO ₂ CH = CH ₂ - ^ RO-CH ₂ CH ₂ SO ₂ CH ₂ Ch ₂ -OR ¹

The bis-ethylene-unsaturated-ether-sulfone obtained can then π it a solution of a peracid in what is described below Way to be implemented.

A syriii ^ etrischeri and asymmetrical epoxy dietary sulfones can be obtained by reacting an alkali metal sulfide with eixie: 2. Chloriiydrin with increased. Temperatures for the production of 3is- (14 / -oxyall-: yl) -3ulfide are produced; the latter can then be converted into the ilatrium salt and this can be converted into an ethylenically non-reactive halide at elevated temperatures to form the bis-ethylenic-uiigesäxtigem-ether sulfide. The following equation illustrates this manufacturing process:

009813/1614

Na ₂ S + 2 CH ₂ -Z-CH ₂ (HO-CHg-Z-CHg- ^ S

Na 'V

50-100 °

Cl OH

R ¹ Cl
₂ ^ ₂ S 4 (NaO-CH ₂ -Z-CH ₂ ^ ₂ S

in which Z stands for a simple one connecting two methylene groups: ix \. o-.a / or a divalent saturated aliphatic hydrocarbon and R ^{1 is} a cycloalkenyl, polycycloalkenyl radical, etc. in which the ethylenic bond,)> C = C ' _x , is at least one carbon atom away from the chlorine radical. Then the bid (ethylenically unsaturated ether) sulfide is reacted with at least 4 moles of peracid per mole of sulfide under the working conditions of the epoxidation process described below. In this reaction, the sulfide part, ie -S-, is oxidized to the sulfonyl group, ie -SOp-, and oxirane oxygen is introduced in the place of the two carbon-carbon double bonds of the sulfide.

Various other diepoxysulfones can be produced as follows , / to earth: a conjugated colil hydrogen serving as e.g. 1/5 butadiene, 1,3-hexadiene, cyclopentadiene and alkyl substituted Cyclopentadiene, can contain less than v.5 moles of divinylaulfone per mole of diene at elevated temperatures to a bis (cycloalkexiyl) .julfone implemented. Diepoxidation this Product in the manner described below gives daa the corresponding diepoxysulfone. Various symmetrical and unsyn -.-. Letrics Diejjoxysulfone can still be produced, indü ,, an ilalo ^ enalkene or halo-cycloalkene, such as 3-chloro-

r ~ 2 5 * 7

propene, J-chloro-cyclopenten, j-chloro-tricyclo- ^ 4.3 ^ 0.1 '^ / - dec-

BATH

0 0 9 8 1 3/1 6 U

7-en, S-chloro-oicyclo - / ^^. l_7-nept-2-en and 4-Cnlorcyclonexen, with the. Sodium salt of an Alkeriylmercaptan3 or Cycloalkenyliiiercaptans, ie HSlTa (where R can be an alkenyl or cycloalkenyl radical) under increased Te.-Kjjeratur and preferably using the RSNa in the corresponding .Mercaptan as a carrier, converted to di-unsaturated sulfide. The saturated diaulphide obtained can then be reacted with.

Various other polyecoxides listed above are known to be prepared as follows: eg tricyclo ~ _/ /4.3.0.1 ⁱⁱ J- 7-decen-3-yl-alkenyl ether, tricyclo- ^ 4.3.0.1 »cycloalkenyl ether, tricyclo- / 4.3.ü .1 '^ / - T /.2.2. l7-5-hepten-2-yl-e.-ti.er, Tr icy clo- / T. 3.0.1 ² »? 7-7-decen-3-y 1-alkenoate, tricyclo - ^ / Tjü.i ^ 'v-7-dece: i-3-yl-cycloalkenecarboxylate or tricyclo - /. T.3.0. 1 ² '^ 7-7-decen-3-yl-bicyclo- _; /2.2.i7-5-heptene-2-carboxylate can be mixed with a solution of a psrate, such as perbenzoic acid, perpropionic acid and peracetic acid, in an inert, normally liquid, organic medium, such as ethyl acetate, at a temperature between 25-90 be epoxidized as long as. Oxirane oxygen is introduced in place of all carbon-carbon double bonds of the olefinically unsaturated part of the reaction. Periodic analysis of samples of the reaction mixture to determine the amount of peracetic acid consumed during diepoxidation is carried out in a known manner. Theoretically, in order to achieve a practically complete epoxidation of the olefinically unsaturated reaction participant, at least a chiometric

009813/161 *

Amount of peracid per carbon-carbon double bond of the olefinically unsaturated compound can be used. Ethyl acetate and acetic acid can be removed from the solution of the reaction products, for example by distillation under pressure. If necessary, the remaining product can be fractionally distilled to obtain a Liei-oxysulfons of high purity, u: .. be crystallized, etc.

The olefinically unsaturated .. Ke action participants for their part are made as follows: the diolefinically unsaturated ^ »Tiier, like;:, K Tricyclox /^.^. 0.1 &quot; ^ Lther and

Klnuen produced v, earth, byc: - Implementation of the unsaturated Λ1 i -.-.-) ;: üla, such as alkenol, cycloalkanol, cycloalkenylalkanol, .7. · "Ycloalkenol and Ijicyoloalkenylaiiianol, x" it-! "Icy el open * all ei: i>. :: .. eseiJieit a Lewis acid catalyst, '.vie z.r ·. Bortr * il'uorid, at a temperature in ». Range from 5 ^ to 2 °. Lie

the reaction products are made from a suitable neutralizing agent such as e.jB. I-atrlui:, - cnrtonat or i? Ulverized lime, neutralized, filtered and sc ^; : Lie ^ lioh zur Gewi: uran · ^ des diolefinisch im-ges ^ tti ^ ter · It> era distilled under prevented pressure.

The diolefinic monoesters, such as, for example, tricyclo- / 5.3.0.1 ^ ^ JI -decen-i'-yl-oycloalkene carcoxylate and tricyclo- / 4 *. 3.0,1 »^ -T-aece. ^ - yl-bicyclo- ^. 2. l _ / - 5-heptii-2-carbcxylate,

Λα.1:. '.! Oil
can ge an ethylenically ur.zesfcttigten Ί 0110caroonsäure such as alkenoic, Cycloalrzencarbonsäure, Cycloalkenylalkansäure, BieycloalkencarbonsLVure and Bieycloalkenylalkansäure, "* · dicyclopentadiene and 3- stün.diges 5-bis heating *

009813 / 16U 6ADORiGiNAL

the resulting mixture with stirring to temperatures zv / iücLen 60-120 ° manufactured ./ earth. The reaction takes place in presence a small amount of an inorganic acidic catalyst, such as sulfuric acid or boron fluoride. The received misclmn_ The Pt eaktiona products are then not used with water and soda. solution washed, dried and for the extraction of the diolefini— see Llonoesters - .. nt he prevented.:. Brucii distilled.

The erfiiidunöSgemäi; Some polycarboxylic acid anhyarides include the aliphatic, aromatic and cyeloaliphatic acid anhyarides. Preferably Y / erdea the ätiiyleniscii unsaturated PoljCarbonsaurearjT.ydride, ii ^ sbeaondere the athyleniscn unge a'Ltt temperate Kohlenv / asaerst-üffdi-carboi- ^ i-anhydrides, v / ie, for example, those which have a J-Cl. ₁ ier is i er care stii ^ le-iioche carbon - carbon-LoppelLindur ^ contain. Such polycarboxylic acid aihydrides are, for example, phthalic anhydride, tetrahydrophthalic anhydride, hexahydroi ^ ti: aluminum anhydride, G ^ lorendics. .ureaniihydride, iilaleic anhydride, chlorinated anhydride, dichloroialeic anhydride, citraconic anhydride, isocitraconic acid a / ihid, glutaric anhydride, adipic anhydride, adipic anhydride, succinic anhydride anhydride anhydride, succinic anhydride, acacic anhydride, succinic anhydride, ita anhydride, hexaic anhydride, succinic anhydride hexa-succinic anhydride, it-a-succinic anhydride, it-a-succinic anhydride, dichloroialeic anhydride , Liüthylbuty Ic serious one. "- ureai ^ ydrid, '.,".'; t. y e tr ai It ydropt haisäure annydr id, n-Honeriylcerns-jeiiiLjäurearjiydrid, OctenylternsteinuUureanriydrid, Penteiiylbern3tei..ai-.ureani.ydrid, Prci.ylberns-jeinsäureanLydrid, 4-Nitrophthal3- -ireani.yarid, 1, _i; - i: a _i , ntr _i alin3a.ureani.ydrid, 2,5-h-: i.iii "3äureü.: i :: yirid, 1,.-IIaphthali ^ anhydride, l'etrabrom-.alscurearJi ,, arid, letra ^ odihtr.alsiuro ü:.: ,, drid,-low

009813/1614. --- v ^

alkyl-substituted bioyclo- / 2.2.17-anli / drid and: iethylbicyclo- £ 2. 2. 1 / -hepfc-5-en-2 _t 3-dicarbo: iaic anhydride. It can also polymeric anhydrides or _a e.aischt polymeric anhydrides of sebacic, adipic, pine in- 1, Cyclohexari-l, 4-dicarboxylic, terephthalic and isophthalic acids used v / ground. Maleic anhydride is most preferred.

As stated above, the use of a polycarboxylic acid anhydride as the polycarboxylic acid compound is preferred in the curable preparations. However, mixtures of polycarboxylic anhydrides and polycarboxylic acids can also be used, or the polycarboxylic anhydride can be completely replaced by a polycarboxylic acid. Whether the polycarboxylic acid anhydride component replaces the polycarboxylic acid anhydride component partially or completely, the requirement applies as before that, in addition to the monomeric, ethylenically unsaturated compound, at least one of the components in the curable preparation has an ethylenically unsaturated carbon-carbon bond that is linked to the monomeric carbon-carbon bond , ot, ii ^ iciix _u ou ^! saturated compound is polymerizable, must possess. If a polycarboxylic acid is used instead of the polycarboxylic acid anhydride in the curable system, it is expedient to keep the concentration of the acid so that 0.16-3.0 carboxyl groups are present per epoxy group of the polyepoxide component. The saturated and ethylenically unsaturated polycarboxylic acids (including the polycarboxy-polyester) include the compounds described in US Pat. No. 2,934,508.

009813/1614

The monomeric, ethylenically unsaturated compounds suitable for use in the hardenable compounds according to the invention are those which contain an ethylenic bond which can be made into an ethylene oxide. These iconomeric, kthyleniuck unsö. bt igt en VerMn / Ju ^ en; jind // eiternixi dadurcj— ^ ekerifizeicLnet, that besides the polyn-eri— üiei-baren äthyleniscne .. groups no radio ■ :! One of the groups which are reactive with neighboring Epo ^ j groups or Garooxyl groups are eliminated. Soicne niünoniere ^, ktnyleniüon un _; / saturated connectors ,. 3ind, for example, the mono- and pol / olsfini.jcne :. Hydrocarbons, such as, for example, isoprene, heptene, octene, ionene, butadiene, pentadiene, hexadiene, heptadiene, octadiene, cyclopentene, cyclohexene, cycloheptene, low-alkyl / isucosituated cyclohexene, low-alkyl-substituted cyclohexene, n-cyclohexene, cyclohexene, Propylc / clohe ^ ten, styrene, Allcylcjtyrcl ,. Chlorstyroi, Ät: \. styrene, diethylstyrene, iaopropylatyrene and divinyltenzene; the olefiiiiache .: ^ .ster and ethers, such as divinyl ether, diallyl etxier, li (2-uatenyl) ether, ii (2-p3r.iteriyl) ether, vinyl allyl ether, vinyl isobutyl ether, ethyl acrylate, ethyl crotonate,: \! ethyl : ethyl acrylate, ethyl acrylate, ethyl crotonate, ethyl methacrylate, propyl acrylate, prepyl crotonate, propyl; ethacrylate, allyl crotonate, allyl acrylate, allyl nacrylate, allyl butyrate, dinolethanoate, allyl acrylate, benzoylate, allyl ethylate benzoate, allyl-2-ethylbenzoylate, allyl-2-ethylbenzoylate, allyl-2-ethylbenzoylate, allyl-2-ethylenoethanoate, allyl-2-ethylbenzoylate, allyl-2-ethylbenzoylate, allyl-2-ethylbenzoylate, allyl-2-ethylbenzoylate, allyl-2-ethylacrylate, allyl-2-ethylacrylate, allyl-2-ethylenoethanoate, allyl-2-ethylacrylate, allyl-2-acylate and alkyl oleate. Other monomeric, αfchyle- ^ niach unsaturated compounds are, for example, triallyl cyanurate, triallylamine, vinyl chloride and acrylonitrile. The iono and polyallyl ethers, the mono- and polyallyl esters and the alkyl acrylates are preferred. Such particularly preferred} monomeric,

009813/1614

Ethylenically unsaturated compounds are, for example, diallyl phthalate, triallyl cyanurate, ethyl acrylate, styrene and methyl methacrylate, with styrene being most preferred. iöche and / or j;. henolische hydroxyl groups are included, the term ¹¹ PoI ^ oil "comprises ... ore ./ert weight alcohols and polyhydric -Piienole · polyhydric alcohols, ie.. Compounds consisting only of koiiluia, hydrogen, and oxygen are particularly preferred. Suitable polyols are, for example, die.alil-hatlachen and cyaraliphatic polyhydric alcohols, such as, for example, ethylene glycol, lithium glycol, polyethylene glycols, propylene glycol, polyprorylene glycols, polyethylene polyethylene glycols, butylene glycols, butylene diols, butylene diols, ethylene glycols Pentanediols, the pentanediols, 1-ethyl-1, 3-hexanediol, the hexanediols, 2-iuethoxy-II, 'jj-di ^ ethyl-1, 5-peixta ^ diol, 12,13- tetraoo3anediol, poly glycerin, 1, 1, 1-Tri:;: e vr.ylolpropai :, Tri-. i-: etix-; lolphe- * ', lally lather, pentaerythritol, hcrbit, the pol _v , vinyl alcohols ,, the octenediols, Γ-ie cyclopentaudiols, the cyclohexanedicle.,. die .low alkylsubst it alerter. Cyclohexanediols, inositol, iri-ethylolbeuzol; and the ::. Ehr.vertigeii Ihenole, such as. Resorcinol, Ereiizkatec-iiu, pyrogallol, hydroquinone, dihydroxytoluenes, ripzcyxylol, P.iv3- (4-ox _t piieuyl) ~ 2, 2-propaii, 3is- (4-oxy-r i-hei: yl) -methane , 1, b-Iiaplit ::. Alindiol and the. Polyvalent phenclr.cr; .. aldehyde condensa "v; icn3j _: jroduirte. Also, the all: ylenoxyd ^ -Addul: ie., -

vie e.g. adducts, av.s. Ethylene oxide and propyl oxide ::: \ t . ά§4 - ot-er. ■. more-

/ i ^ eii Alliohaben or.:. eLrv.'ertije-i Phe ^ cl.en, sir.d _iä

se-ir suitable jc.vie Mischun ^ e :: ve :, r-

00 9813/16 1 4.

BAD OHiGJNAL

Suitable polyols are those which are polyhydric by reaction Alcohols or polyhydric phenols containing at least 3 hydroxyl-> contain groups, with an aliphatic monocarboxylic acid described below to form your esterified Mixture can be produced with an average of at least two free hydroxyl groups. For example, 1 mole of glycerine can be mixed with 1 Moles of an aliphatic monocarboxylic acid reacted and so one Mixture of glyceridesJ the average of two free. Hydro- ' contains xyl groups per glyceride molecule in the reaction product,

are obtained, as polyol components in & s curable systems are also suitable polyols, which are obtained by reacting poly-, epoxides, such as limonene dioxide. 4 ~ vinylcyclo.hexenedioxyd, bis (2,3-epoxycyclopentyl) ether, dicyclopentadiene dioxide, divinylbenzene dioxide, 3,4-epoxy-6-methyIcyclohexylmethy1-3,4-ej-oxy-ö-ffiethylcyclohexanecharöoxylat, I) iethylene glycol (3,4-epoxycyclohexanecarbox / ldt), bis (3,4-epoxycyclohexy! Methyl) pimelate and Ί, 1,1-trimet: .ylolpropari-tris- (3 »4-epoxycyclohexanecarboxylate), with an aliphatic monocarboxylic acid, such as hexanoic acid, caprylic acid, lauric acid, capric acid, myristic acid, oleic acid, linoleic acid, oleostearic acid, licanic acid, ricinoleic acid, hexenoic acid, hexadienoic acid and octenoic acid, preferably at leu-i-eratures of 25- ^ 50 ° with or without a catalyst will. At the. The lower limit is the concentration of the II on ο carbon acid used, the amount that is sufficient for the reaction .. \ it all epoxy groups contained in the polyepoxide and it yields an esterified product, the ester groups, 0, and formed hydroxyl groups, -OH,

- 'ti

009813 / 16U =

contains. It should be noted that for each epoxy group reacted with a carboxyl group, an ester group and a hydroxyl group are formed. The upper limit for the concentration of ivionocarboxylic acid is the amount required to react with all epoxy groups contained in the polyepoxide plus the amount required to esterify all but two hydroxyl groups formed. Therefore the reaction product can be referred to as a "polyvalent polyester". For example, if the polyepoxide is a diepoxide, such as 4-vinylcyclohexenedioxide, then the concentration of the monocarboxylic acid required for the above reaction is that amount which creates a ratio of one carboxyl group of the acid per epoxy group of the diepoxide. To put it more simply on a molar basis: 2 moles of acid per mole of diepoxide are required. In this example the product obtained would be a diol diester. If the polyepovc / d is, for example, a triepoxide, such as 1,1,1-trimethylolpropane-tris ~ (3 * 4-ejJOχycyclohexanecarboxylate), then the required iJiadest concentration of the monocarboxylic acid is that amount which corresponds to a ratio of one carboxyl group of the acid per epoxy ~ gruj ^ re "which creates triepoxide. In molar terms: 3 moles of acid per mole of triepoxide are necessary to obtain a triol triester. It is therefore evident that 4 moles of acid per mole of triepoxide would yield a diol tetraester. In this example, the upper limit would be Monocarboxylic acid an amount which creates a ratio of 1.33 carboxyl groups of the acid per epoxy group of the triepoxide. In order to avoid misunderstandings, the following equation is given:

00 981 3 / 16U BAD CRJCi ^ AL

j O

I ι ti

-σ _ν ο -C-OCR

j 0 + RCOE * ■ |

-C '-C-OH

where the epoxy group is contained in the polyepoxide & oleküT and 0

RCOH stands for the ali ^ natisehe Llonocarboxylic acid. The above Equation illustrates the mechanism by which a ^ rc .- / calibrate a Hydroxyl group and an ester group formed, vex'den.

One embodiment of the present invention "focuses on hardenable and partially hardened preparations (screechable, warning solidifying agents that are viacous liquids or pesticides), which are composed of a ... -aui'fc / t; rb: .iiaung, a monomeric, ath / lenl3cn un- saturated Ye ^r blndung and optionally elr.a: .. Pol / ol admit, wherein the Präpy-race in an inert,.. noriLaler. '/ eiae liquid, organic metal, such as xylene, ilechylisocutylkeson, Bu'aylacetat, ethyl acetate, toluene and Ai ;; ylaoeti ~, are dissolved. The organic compounds dissolved in the examples given above can be used as organic compounds, for example Surface pulls are used, which can then be hardened to hard, tough, scratch-resistant coatings.

The ratio of partially hardened. Earz, d.n. vvari .: solidifying Intermediate product, depends on the organclial medium

of different factors, such as the particular one to be cured Mixture, the degree of partial hardening and the particular organic medium used ..., from. Ia general is a solution of 10-90% by weight of the partially cured

009813/1614

Resin based on the total weight of partially cured Resin and organic medium, suitable, but 40-70 wt.? of the partially cured resin are preferred. Furthermore, the non-hardened preparations in the above-mentioned organic medieli dissolved, applied to surfaces and are then thermoset to form hard, tough coatings. The solution should be your non-hardened or partial hardened preparation tend to "run" when applied to surfaces, so a common wetting agent and / or thixotrcpes can be used Means are added to make a more uniform coating to ensure on the surface.

In the following examples, the Barcol hardnesses were to a.:! Barcol-Im ^ ressor GYZJ-934-1 at a part of 24 ° beatim-t. If not stated otherwise, the examination will be carried out or description of the resins at room temperature, i.e. 24 °. The temperatures of the heat resistance were determined according to AST1 £ - Proceed with D-648-45T determined.

009813/1614

example 1

7.6 g of 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4- '. epoxycyclohexanecarboxylate and 2.4 g of maleic anhydride were mixed in such amounts that 1.0 carboxyl groups of the maleic acid ' anhydrides per epoxy group of the ö-methyl - '^^ - epoxycyclohexylmethylö-methyl-J ^ -epoxycyclohexanecarboxylates were present, and the mixture heated to 50 °; at this temperature it was homogeneous. After cooling to 25 °, 0.07 g of methyl ethyl ketone peroxide (as a 60 wt .- ^ solution in dimethyl phthalate) were added with stirring, add and then to the mixture obtained 0.02 g cobalt naphthenate

added. After stirring for intimate mixing, the mixture was allowed to stand for 24 hours at room temperature, ie about 24 °, whereupon a viscous liquid was obtained.
Example 2

6.1 g of 6-methyl-3 ^ -epoxycyclohexylmethyl-o-methyl ^, 4-epoxycyclohexane carboxylate and 1.9 g of maleic anhydride were mixed in such amounts that 1.0 carboxyl groups of the maleic anhydride per E ^ oxy group of the e-methyl ^^ - epoxycyclohexylmethyl-6-methyl-3,4 - epoxycyclohexanecarboxylate templates and this mixed *! heated to 50 ° until homogeneous. After cooling to 25 ° the following ingredients were added to the mixture / 2.0 g of styrene in such an amount that an ethylenic bond per ethylene bond of maleic anhydride existed? 0.07 g . Methyl ethyl ketone peroxide (as a 60 wt .- # solution in dirnetnyl phthalate) and 0.02 g cobalt naphthenate. Within 5 minutes at 25 the mixture obtained gelled. * ·

009813/1614

In comparison to Example 1, the gelation took place in an unexpectedly short time at room temperature due to the incorporation of styrene into the curable preparation. Example 3

O ', 41 g of bis (2,3-epoxycyalopentyl) ether, 0.29 g of maleic anhydride and 0.3 g of styrene were mixed in such amounts that 1.0 carboxyl groups of the maleic anhydride per epoxy group of the bis (2 , 3-epoxycyclopentyl) ether and 0.5 ethylene groups of styrene per ethylene group of maleic anhydride were present. The resulting mixture was heated to about 100-120 ° for about 20 minutes and then to 160 ° for a further 4 hours, whereby a solid, tough, yellow resin with a Barcol hardness of 45 was obtained.
Example 4

4-vinylcyclohexene dioxide (0.45 g) »0.2? g maleic anhydride and 0.28 g of styrene were mixed in such amounts that 1.0 carboxyl groups of the maleic anhydride per epoxy group of the 4-vinylcyclohexenedioxide and 0.5 ethylene groups of styrene per ethylene group of maleic anhydride. The resulting mixture was heated to about 100-120 ° and for about 20 minutes heated to 160 ° for another 4 hours, creating a firm, viscous, orange resin with a Barcol hardness of 50.

009813/1614

Example 5

0.47 g of dicyolopentadiene dioxide, 0.26 g of maleic anhydride and 0.27 g of styrene were mixed in such amounts that there were 1.0 carboxyl groups of calcium anhydride per epoxy group of dicyclopentadiene dioxide and 0.5 ethylene groups of styrene per ethylene group of maleic anhydride. The resulting mixture was heated to about 110-120 ° for about 30 minutes and then to 160 for a further 4 hours to give a solid, tough, yellow resin with a Barcol hardness of 25. Example 6

0.45 g of dipentenedioxide, 0.21 g of maleic anhydride and 0.2-3 g of styrene were mixed in such amounts that 1.0 carboxyl groups of maleic anhydride per epoxy group of di / pentenedioxide and 0.5 ethylenic groups of styrene per ethylenic group Maleic anhydride templates. The resulting mixture was heated to about 110-420 ° for about 20 minutes and to 160 ° for an additional 4 hours, giving a solid, tough, yellow resin with a Barcol hardness of 25. Example 7

2,3-Epoxypropyl-4-oxatetracyclo- ^ S.2.1.0 ³ » ⁵ .0 ² * ^ I- undec-9-yl ether (0.52 g), 0.23 g maleic anhydride and 0.25 g Styrene were mixed in such amounts that there were> 1.0 caroxyl groups of maleic anhydride per epoxy group of the ether and 0.5 ethylene groups of styrene per ethylenic group of maleic anhydride. The mixture obtained was heated to about 100-120 ° for about 20 minutes and to 160 ° for a further 4 hours, whereby a solid, tough, colorless resin with a Barcol hardness of 35 was obtained.

0 09813 / 16U ^BAD original '

Example 8

0.64 g. 5- (6 ^f -Methyl-5 ', 4'-epoxycyclohexyl) -2,4-dioxaspiro- ^ 5.57-8.9 ~ epoxyundecane, 0.17 g maleic anhydride and 0.19 g styrene were mixed in such amounts that 1.0 carboxyl groups of the maleic anhydride per epoxy group of the diepoxide and ³ HXi Ü, ethylene groups of styrene per kthylenic group of the lialic acid anhydride were present. The resulting mixture was heated to about 100-120 ° for about 2c minutes and to 160 ° for a further 4 hours, whereby a solid, tough, yellow resin with a Barcol hardness of 55 was obtained.
Example 9

1,4-butanediol-bis- (6-: neti _J .yl-5 ^ 4-epoxycyclohexylmethylether (0.65 g) 0.16 g maleic anhydride and 0.19 g styrene were mixed in such amounts that 1.0 carboxyl dea maleic anhydride per epoxy group of the diepoxide and i w * 0.5 äthylenisohen groups of the styrene per ethylenic group of the maleic anhydrides present. the mixture was heated for about 50 minutes at about 100-120 ° C and further 4 hours at 160 ° to give a solid, hard, orange-colored resin with a Barcol hardness of 10. Example 10'bia 14

Dicyclopentadiene dioxide and maleic anhydride were added to various test tubes in such amounts that 1.0 carboxyl groups of the anhydride were present for each epoxy group of the dioxide and the mixture obtained was heated until a uniform melt was obtained. The mixtures were then cooled to about 3% and an ethylene-iso-unsaturated monomer added in a small amount that 0.8 ethylene groups per ethyV

009813/1614 - * ί

BAD ORfGINAL

lenischer group of maleic anhydride was present. Then 0.1 wt% benzoyl peroxide based on the total weight of the charge was added. Hacr. After gelation, the systems were 6 btuiiuc .ι aiu ΐυθ ° heated. The results are in the following

Table specified:

Be is ρ. Ethylenic Lionomeres description of the resin

10 Iriallylainin hard, firm

11 Triallyl cyanurate * hard, solid

12 χ.-Chloratyrol xxart, solid

13 ch -Liothylotyrol nart, solid

14 Bivixylbenzene hard, feat

B e i s ρ i e 1 15

Bis- (2, ^ -epox ^, cyclopentyl) -Lther and Itaconaüureamihydrid was :, ii aolche. · - ..oxi ^ e ^ .e..i3cht, dal: 1.0 Cj.rbojc _u lgruj .; _x .en des Itacor.Sciureaxiliydrida _; ru üpoxygruppe deu bis - (^, 3-epoxycj · clo- ^ ■ ei ^ tylJ-Lthera vorlagen, iuiacr.lie ^ eiid an aolcne! narrow styrene was added to this I / iGung, so that; 0.6 ethylene group l -vo äthylexiioCxier group of Itacoxi.a.-urea / iiiydr .. as templates, and the -.lischun.j obtained; about L ₁ O hours et v / a 120 °, and more .. hours at 16l ° -3ri .itst. So a:., solid, tough resin was en.old en.

e.-itadieiidiioxyd,. ;. . 'j-aüurearüiydrid and Divinylcexizol were in selche:'. I.Ieij. ^ Ex. It is true that 0.9 caroxyl groups dea A: -: - _{and '} uri-io per ipoxy group of the Licyclopex.tadiendioxyds and v ** k 1, 0 Lti ^ leiiiacl-ie group., Dea Divinglbenzola pro äthylenisciier Gr -ppe des;, :::. Ydrid ^ templates. The obtained I / Iischung was about 2 hours a; i 'et.vu 12L ^C and a further 8 hours at 1ί: 0 he ^ο - .. iczt' Wciurci. ο Ic fea ";'=s," urtea Ilarz eri. altexi became.

0098 13/1614

Example 17 bis

A different one was put into different test tubes P ο Iy ep oxy d and maleic anhydride given in such amounts, daiä 1.0 carboxyl groups of the anhydride per epoxy group of the Polyepoxyds were present · Then styrene was added to this mixture in added in such an amount that 1.0 ethylenic groups per atliyleiiiiiciier group of maleic anhydride »were present. After that was 0.1% by weight of benzoyl peroxide, based on the total weight the charge »added and the resulting mixtures -then 2 hours at 80 ° and a further 8 hours at 90 °. BIe

Results are as followsί Beiap. Polyepoxide

Description of the resin

3-

ethylene glycol-bis-C / oxatetra-

tough, hard solid undec-8-yl ether

3,4-Epoxy-6-methylcyciohexyl ~ tough, hard solid methyl-3,4-epoxy-6-methylcyclohexane carb oxyIate

4-vinylcyclohexenedioxide

Bis (2,3-epoji.ycyclopentyl) -

ether

4-Vinj''lcyclohexenedi oxide Bipenten Dioxide

Bis- (3 1 4-epoxycyclohexyl) sulfone

Tetraethylene glycol bis-coethyl-3,4-epoxycyclohexane carboxylate)

tough, hard solid tough, hard solid

solid, hard solid x'ester, hard solid solid, tender solid

solid, hard solid

BAD ORlGJIMAL

009813/1614

Example 25_

100 g Epon 1004 (trademark of Shell Ciieiaical Corp. for a polymeric polyglyeidyl polyether ve:;. Bis- (4-oxyyceuyl) 2,2- ^ ropan uit a *;. Epoxydjx.iuivalentgewicnka — Bex'sien from 905-905 and eirieD. Erweichun ^ sbereicii of 95-105 °) and 25 g iialeins & anhydride were placed in a Reaktionsa-ef & L · and heated to about 100 ° until dissolved. The isolation was extremely vialcos and difficult to mix under the conditions used. A higher term was not used because of the lack of a premature gelation of the system. Then • 10 g of styrene and 0.005 g of eenzoyl peroxide were added and the system was stirred vigorously. The styrene was, however, pure and contained non-toxic bubbles. The solution was poured into an iron mold and then heated to 200 ° for 6 hours for 120 and a further 6 hours. In this way, a yellow, undurciioichtigea, narcotic product was obtained, which contained a number of lreiciie bubbles ^ n etv / a 40-45 ^ nd a ..cr .-. oü. ^ ti -j speed of 108 °.
Example 26

1.0 g of bis- (3j4-öi.o> cycyGlonex _J l ^ ethyl) -aaleate _f u, 45 g of 8-methyl-4-oxatricyclo- ^ 5'.2.1.0 ^fO _ ^ - dec-S-en - ^ _r 5-dioii and 0.26 g of styrene were se ^ ischt ux ^ -s. ice-cream for high quality "A gelation"; the resulting liischrm ^ took place internally voxi 64 minutes at 120. Then, I hardened for 7 hours at 120 ° and a further 6 hours at 160 ° and thus obtained a hard, tough Hars with a Barcol hardness of 51 »

bath

009813/1614

Example 27

1.0 p of bis (3,4-epoxycyclohexyl.:. Etiiyl) maleate and 10 g of adipic acid were mixed and finally heated until homogeneous. Gelling of the mixture was visible after 6 hours at 120 °. This was followed by post-curing for 7 hours at 120 ° and a further 6 hours at 160 ° and a hard, tough resin with a Barcol hardness of 40 was obtained.
Example 26

1, g iii3- (3 »4-eppxycyclonexyl: i.etxiyl) maleate, 0, U; g of adipic acid and 2 g of styrene have been poured, heated and then heated to homogeneity. A Gelierun _{above sea level} - this "ischung took place within halo ν η 49 Llinutei: at I2C ° Lan, v / urde 7 hours at 120 °, and further 6 hours at 160 ° :: -lacn ^ enLrtet and so a hard!... zenes resin: .. obtained with a Barcol hair of 3b , eg 29

1.0 g Bis-iJ ^ -e ^ oxyc ^ clohoxylüietnyli-fu / ^ arat, U ₁ Z £ Px.t .alsäureanliydrid and C, ^ g * xet: _v i: .. et: .acrylat was mixed un. i ansciilie ^ eiid heated _{to hoact t ieiiity.} Uann was 7 hours at 120 ° and a further 6 hours ;: at 160 ° night:; hardened and a solid, tough resin was obtained.
Example 30

1.0 g of Pis-0,4-epoxycyul-ohexyliethyl) itaconate, 0.2 g Glutaric acid an: ydri I and 0.3 g of diallyl phthalate were mixed and axi3Ci-Iiei.end tis heated to the Hoiuogeiii ^ ct. Lann -, vurde "~ oxuxiden at 120 ° and another ό hour .: post-cured at 160 ° and so on eir. hard, tough resin.

BAD ORlQmM. 0 0 9 8 13/1614

Example 31

178.2 g of dicyclopentadiene dioxide, 64.0g maleic anhydride and 9.9g 1,1,1-trimethylolpropane given in such amounts that 0.6 carboxyl groups of the anhydride and 0.1 hydroxyl groups of 1,1,1-trimethylolpropane

per epoxy group of the dioxide, and the resulting mixture heated to an admixed melt. Then the Mixture cooled to about 35 ° and 67.9 g of styrene in such a Amount added so that there were 1.0 ethylene groups per ethylene group of 3 maleic anhydride. Then 0.034 g

Benzoyl peroxide was added as a 5% strength by weight solution in hexanone and the obtained, mobile liquid mixture in six aluminum containers

poured. Each container contained approximately 35 grams of the mixture that

approximately
then heated to 60 / 1.5 hours and then to 200 for a further 6 hours

became. Gelation took place after about 1.5 hours at 60 °. The obtained, hard, tough, resin-like products were cut into uniform bars of about 0.6 I, 2 12.5 οι: ι etv / a, each weighing about 13 g. The bars were then heated to 260 ° C. for various lengths of time, the weight loss being calculated at specific time intervals. The data are given in Table 1:

Table 1 std at 260 ° jo Weight loss heat resistance; ⁰ C.

0 0 170

26 '2.8> 295

49 4.6> 295

100 5.9 289

192 8.5 ^J 280

500 13.5 272

bath

0 0 9 8 13/1614

Example 32

Example 31 was made using the following procedure. conditions repeated:
Component weight in g equivalent ratio

Dicyclopentadiene dioxide 153 ,1 1.0 (Epoxy) Maleic anhydride 73 , 9 • 0.8 (Carboxyl) 1, 1,1-irimethylolpropane 16 0.2 (Hydroxyl) .Styrene 77 1.0 (1)

(1) = ratio of the by the amount of monomeric, ethylenic ethylenic groups created by the amount of unsaturated polycarboxylic acid anhydride created ethylenic groups

Gelation took place after 75 minutes at 50 °. after the finished bars were tested according to Example 31, the following results were obtained:

Table 2

3td at 260 ° < & Weight loss Heat resistance j ⁰ C. O 0 182 26th 2.6 > 295 49 4.7 285 100 6.1 286 192 8.6 279 500 13.7 266 By S P i e 1 33

Example 31 was made using the following ratios repeated!

Korn 'onente Weight in g equivalent ratio

Dioyclopentadiene dioxide 136.6 1.0 (epoxy) Maleic anhydride 81.6 1.0 (carboxyl) 1,1,1-trimethylolpropane 14.7 0.2 (hydroxyl)

Styrene 87.1 1.0 (see footnote 1 above)

Benzoyl peroxide 0.044

0 0 9 8 1 3/1 6 U

Gelation took place after 65 minutes at 50 °. The finished Bars were then tested according to Example 31 and the following Results obtained:

Table 3

std at 260 ° fo weight loss 0 0 26th 2.6 49 5.2 100 7.0 192 9.4 500 14.7 B e i s ρ i e 1 34

Heat resistance; ⁰ C.

215

285 285 277 255 256

Example 31 was repeated using the following ratios:
Component weight in g equivalent ratio

Dicyclopentadiendiox / d 123.7 1.0 (epoxy)

Maleic anhydride 8b, 7 1,2 (carboxyl)

1, 1, 1-trimethylö5propane 13.4 C _t d (hydroxyl)

Styrene 94.1 1.0 (see footnote 1 above)

Benzoyl peroxide 0.047

Gelation took place after 95 minutes at -ί-0 °. The finished Bars were tested as in Example 31 and the following results achieved:

O,

Table 4 Wuriefest std at 260 ° io weight loss 220 0 0 293 26th 3.0 274 49 5.6 276 100 7.7 270 192 10.0 239 500 15.4

00 98 13/16-U

Example 35

Example 31 was repeated using the following ratios:
Component weight in g equivalent ratio

1, 0 (epoxy)

1.4 (carboxyl) 0.3 (hydroxyl) 1, Ü (see footnote 1 above)

Dicyclopentadiene Dioxide 110.7

Maleic anhydride 92.5

1,1,1 -Triynethylolpropane 16.2

Styrene 9d, 6

Benzoyl peroxide 0.049

Gelation took place after 75 minutes at 40 °. The finished Bars were then tested according to Example 31 and the following Results obtained:

Table 5

std at 260 ° C.
J 36 6 weight loss Heat resistant 0 0 244 26th 3.4 285 49 5.6 275 100 8.0 273 192 10.3 264 500 15.6 230 example

Example 31 was repeated using the following ratios:
Component weight in g equivalent ratio

Dicyclopentadiene Dioxide 102.1 Maleic Anhydride 97.6 1.1, 1-Trimethylolprcpane 16.6

Styrene 103.7 benzoyl peroxide 0.052

1.0 (epoxy)

1.6 (carboxyl)

0.3 (hydroxyl)

1.0 (see footnote 1 above)

Gelation took place after 75 minutes at 40. The finished -. Bars were then tested according to Example 21 and the following results were obtained:

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BATH ORIGINAL

260 ° - 44 - 37 Table 6 std at ° / Ό weight loss O 0 26th 3.8 49 6.6 100 8.8 192 ρ i e 1 11.0 500 16.5 By S

V / heat resistance; G.

228 286 264 272 262 239

Example 31 was repeated using the following ratios:
Component weight in g equivalent ratio

1.0 (epoxy) 0.8 (carboxyl) 0.2 (hydroxyl) 0.25 (see footnote 1 above.

Dicyclopentadiene Dioxide 93.5

Maleic anhydride 44.6

1,1,1 -Tr -L. ethylolpropane 10.1

Styrene 11.8

Benzoyl perox ^ d 0.0056

Gelation took place after 4.5 hours at 50 °. The finished ears were then tested according to Example 31 and the following Results obtained:

Table 7 Heat resistance; ° C <

210> 295> 295

288

Example 31 was made using the following ratios repeated:

hours at 260 ° 1 ° 0 38 Weight loss 0 1 25th 3 ,8th 49 7th , 4 97 , 4 B e i s ρ i e 1

0 0 9 8 1 3/1 6 U

I'Ml

component Styrene Weight m 12th Equivalent ratio (Epoxy) - dicyclopentadiene
dioxide Benzoyl peroxide 86.9 1.0 (Carboxyl) 'Maleic anhydride 41.6 0.8 (Hydroxyl) 1,1,1-trimethylol 9.4 0.2 propane (see footnote 1 ob ι 22.1 0.5 0.01

Gelation took place after. 4.5 hours at 50 °. The finished Bars were tested according to Example 31 and the following results achieved:

at 260 ° Table 8 Heat resistance; ⁰ C. hours 0
25th
49
97
is ρ i e 1 ° / o weight loss 215
> 295
> 295
293 " B e 0
1.5
2.5
6.7
39

Example 31 was repeated using the following ratios:
Component weight in g equivalent ratio

Dicyclopentadiene dioxide 8], 4 1.0 (epoxy)

Maleic acid aniiydr id 33.9 0.8 (carboxyl)

1.1, I-trimethylolpropane 8.8 0.2 (hydroxyl)

Styrene 30.9 0.75 (see footnote I)

Benzoyl peroxide 0.0154

Gelation occurred after 2 hours at 50. The finished bars were then tested according to Example 31 and the following Results obtained:

Table 9 W <. .rmef esti eke it : ⁰ C. std at 260 ° fo weight loss 227
> 295
293
285 BATH ORIGINAL 0
25th
49
'97 0
1.5
2.5
6.2

00 98 1 3 / 16U

Example 40

Example 31 was made using the following ratios repeated:

Component weight in g equivalent ent ratio

Dicyclopentadiene dioxide 72.0 1.0 (epoxy) maleic anhydride 34.4 0, b (carboxyl) 1,1,1-trimethylolpropane 7.8 0.2 (hydroxyl) Styrene 45.8 1.25 (see footnote I) benzoyl peroxide 0.0224

Gelation took place after 2 hours at 50 °. The finished bars were then tested in Example 31 and the fol Results obtained:

Table 10

std at 260 ° $> Weight loss Wäri-iefeatig ^ ej-c; C.

0 0 196

25 1.6 290

49 2.3> 295

97 "5.7 264

Example 41

Example 31 was repeated using the following ratios:
Component weight in g equivalent ratio

Dicyclopentadiene dioxide 6o, ^ 1.0 (epoxy)

Maleic anhydride 32.6 0, c (carboxyl) 1,1,1-trimethylolpropane 7.4 u, 2 (hydroxyl)

Styrene 51.8 1.5 (see footnote 1)

Benzoyl peroxide 0.026

Gelation took place after 75 hours at 50 °. The finished ' Bars were then tested according to Example 31 and the following results were obtained:

009813 / 16U

Btd at 260 ° ■ /! ■ weight loss heat resistance; ⁰ O.

0 0 165

25 1.6> 295

97 5.6 273

Example 42

Example 31 was made using the following compounds repeated in the given circumstances:

Component weight in g equivalent ratio

Dicyclopentadiene dioxide 222 '1.0 (epoxy) maleic anhydride 106 ü, i (carboxyl) 1,1,1-trimeth.yloluethane 22 Ό, Ζ (hydroxyl)

The liquid obtained was heated to 60 ° for 0 hours, 100 ° for 6 hours and to 160 ° for a further b hours. Gelation occurred during maturation at 100. The finished bars were tested according to Example 31 and the following. Results achieved:

Table 12 hours. at 260 °. jo Weight loss heat resistance; G.

0 0 1äü

25 3.3> 295

50 6, fa /> - 2o3

75 6.2 265

100 9.5

150 11.5

236 15.7

This βίβχίβΐ 42, ixi which the monomeric, ethylenically unsaturated compound is missing, can be compared especially with the above examples 32 and p7-4'l. The incorporation of the monomeric, ethylenic unsaturated compound, .'ύ, in Examples '32 and the Ldsuneatea- ^ e— temperature in example 4ü / -about 5C Όβτπι ^. Elation took place in the case of preparations which contain the mononsre, kthylenisci. u :. ₅ -e saturated connection- ^ dun. =; e ^ 'ciihalten i "i Vei'ä'leiCii for example 42 olir.e this Loit ^ o.ierite

009813/161 * BAD '

in a shorter time and at lower temperatures. More importantly, the monomeric, ethylene-unsaturated component provided a tough resin with less weight loss than the resin made without an ethylene-unsaturated component.
Example 43

Beio ^ j-el 31 was repeated using the following compounds:
Component weight in g equivalent ratio

1.0 (epoxy) 1.6 (carboxyl) 0.2 (hydroxyl) 1.0 (see footnote 1)

Dicyclopentadiene Dioxide 25.9

Maleic anhydride 24.9 1,1,1-trimethylolpropane 2.8

Styrene 26.4

Methyl ethyl ket oilier oxide 0.016

Cobalt napkinate (6- <each - 0.002

7'ige Kooalt solution)

The mixture obtained was left to stand for about 12 hours at room temperature, ie about 23 °. A hard, tough resin with a Barcol hardness of 50 was thus obtained. This BEIS JIEI ₁ illustrates the preparation of a highly hard resin only durcn curing the system at room temperature. Example 44

The following preparation was produced according to Example 31:
Component . Weight in .g equivalent ratio

Dicyclopentadiene Dioxide 19 »3

Kalein & Ureanhydride 9.2

1,1,1-trimethylolpropane 2 _f 1

Methyl methacrylate 9 »4

Gumol hydroperoxide 0.094

Cobalt ^ iai-htnenat (as Co) 0.002

1.0 (epoxy) 0.8 (carboxyl) 0.2 (hydroxyl) 1.0 (see footnote 1)

009813/1614

bath

The resulting mixture was heated to 90 ° for 6 hours, 150 ° for 3 hours and 200 ° for a further 4 hours, whereby a tough resin with a Barcol hardness of 61 was obtained. Example 45

The following preparation was produced according to Example 31:

Component weight in g equivalent ratio

Dicyclopentadiene Dioxide 19.3 1.0 (Epoxy)

Maleic anhydride 9.2 0.8 (carhoxyl)

1, 1, 1-IrimethylQlpropane 2.1 0.2 (hydroxyl)

Ethyl acrylate 9.4 1.0 (see note 1)

Cuinol hydroperoxide 0.094

Gobalt naphthenate. 0.002

The resulting mixture was "poured into a mold at room temperature and then heated to 90 ° for 6 hours, to 120 ° for 6 hours, to 150 ° for 3 hours and to 200 ° for a further 4 hours. A tough resin with a Barcol hardness was thus obtained obtained from the 61st after 25 hours of treatment at 260, the weight loss of this resin was about 3 fö, its heat resistance was Grüsser than 295 ° · example 46 to 51

0, ü g of dicyclopentadiene dioxide, 0.5 g maleic anhydride and 0.1 g 1,1,1-trine tnyLolpropaii given in such amounts that 1, 0 carboxyl groups of the anhydride and 0.2 hydroxyl groups of 1,1,1-trimethylolproijans per epoxy group of the dioxide. The mixtures obtained were heated to a uniform melt until then cooled to about 35 and an ethylenically unsaturated one Monomer added. Then 0.1% by weight of benzoyl peroxide was purchased on da-j weight of the entire charge. After Göiierung the systems were heated to 160 ° for 6 hours and the

achieved the following results:

BAD ORJGiNAL

009813/1614

Example,
No.

Ethylenic monomer weight in g

Table 13

Setting time; Minutes at C.

Description of the resins 3

46 triallylamine

47 triallyl cyanurate

48 p-chlorostyrene

49 06-methylsxyrene

50 divinylbenzene

51 Diving! Benzene

0.23 0.40 0.70

0.60

0.30 0.60

2.2
1.0
0.5

2.1
1.0
0.5

2.0
0.5

2.0
0.5

50

80

120

50

80

120

50 80

5ü

ÖG

hard, tough

firm, tough, Barcol hardness 40 firm, tough, Barcol hardness 50

firm, tough, Barcol hardness 38

firm, tough, barcol hardness 50 firm, tough, barcol hardness 43

- 51 Example 52

0.8 g of dicyelopentadiene dioxide, U, 5 g of itaconic anhydride and 0.1 g of 1,1,1-trimethylolpropane were placed in a glass beaker and the mixture obtained was heated until it melted uniformly. The mixture was then cooled to about 35 °, 0.5 g of styrene and then 0.1% by weight of benzoyl peroxide, based on the weight of the total charge, were added. Gelation occurred after 1.8 minutes at 50 ° and a further 1 minute at 80 °. The system was then heated to 160 for 6 hours to obtain a strong, tough resin with a Barcol hardness of about 5 <~>. Example 53

0 g of dicyclopentadiene dioxide, 0.5 g of aconitic anhydride and 0.1 g of 1,1,1-trinethylolpropane were placed in a test tube and the mixture obtained was heated until it melted uniformly. The mixture was then cooled to about 35 °, 0-5 g of styrene and then 0.1% by weight, based on the weight of the total charge, benzoyl peroxide was added. Gelation took place after 9 minutes at 80 °. A strong, tough, resin with a Barcol hardness of 47 was thus obtained.
Example 54 to 60

A differentiation was made in different test tubes.

Liches polyepoxide, maleic anhydride and 1,1,1-trimethylolpropane given in such amounts that 1.0 carboxyl groups of the Anhydride and 0.2 hydroxyl groups of 1,1,1-trimethylolpropane were present per epoxy group of the polyepoxide. The mixtures obtained were heated to hosGgenität, cooled to about 35 ° and then styrene was added. Then 0.0014 g of benzoyl peroxide was added

^{009813 / 16U} "BAD ORIGiWL

added and the resulting mixtures 0.5-5 »O hours at 50 ° held; · gelation took place during this time. Then these mixtures were 1 hour at 120 ° and a further 2 hours heated to 160 ° and achieved the following results:

00 981371614 '^

Tabel

Beisώ. Polyepoxide

Weight in grams

Poly-maleic 1,1,1-triepoxy acid methylol anhydride propane

Styrene Description of the resin

Ethylene glycol bis = r (3-oxatetracyclo-, / 4.4.1 '» ^lu .0 ^' j / -

undec-8-yl-ether

6.17

3,4-epoxy-o-methylcyclohexyl-5,6 methyl 3,4-epoxy-D-methylcyclohexane carboxylate

4-vinylcyclohexenedioxide 3.89 bis (2,3-epoxycyclopentyl) ether 4.52

4-vinylcyclohexene dioxide 4.08

Dipentene Dioxide 4.83

Bis- (3,4-oxycyclohexyl) - 5.4

sulfone

1.71 0.31 1.96 0.36 2.72 0.50 2.46 0.44 2.64 0.48 2.26 0.51 2.05 0.37

1.81 tough, Barcol hardness 58

2.08 tough, Barcol hardness 52

2.89 tough, Barcol hardness 49

2.58 tough, Barcol hardness 62

2.80 solid, Barcol hardness 50

2.40 solid, Barcol hardness 55

2.18 solid, Barcol hardness 62

- 54. - Example 61 to 65

The procedure of Examples 54-60 was followed by the following Exceptions repeated: the mixtures were made at y5 ° for Brought to gelling. The curing was as follows: 2.5 hours at 95 °; 4 hours at 120 ° and 6 hours at 160 °. There were achieved the following results:

009813/1614

Belsp. Polyepoxide No. Table 15
Weight in. Grams

Poly-maleic 1,1,1-triepoxy acid ethyiol anhydride propane

Description of the resin

Styrene

61

62

03 64

65

3, ^ - Epoxy-o-methylcyclohexylruetnyl-p ^ -spoxy-ö-ull aGzancardoxylate

4-vinylcyclohexene dioxide

3,4-EvOxy-i-methylcyclohexylme t liyl-3,4 - <-: j .; oxy-1 -methylcyclohexaacarboxylate

Tetraetriylene glycol bis (3.4-6.9

ü uozy-o-methylcycloiiexancarboxyiat) 1.8

1.9

, 4

1.9

4th , 0 ^ά , 3 0 , 6 2 , 5 3 » ^C 2 , 7 ρ , 7 2 ,8th 5 , 5 1 , 9 0 , 5 2 ,1

1.4

zuh, Barcol-Haxte 49

zäii, Barcol hardness 59 tough, Barcol hardness 62 tough, Barcol hardness 41

hard, tough + Barcol hardness

cn ο (J)

- 56 Example 66

10Og Epon 1004 (trademark of Shell Chemical Corporation

ration for the polymeric polyglycidyl polyether of bis (4-oxyphenyl) -2,2-propane with an epoxy equivalent range of 905-985 and a softening range of 95-105) and 25 g of maleic anhydride were placed in a reaction vessel and the obtained The mixture is heated to about 100 ° until it dissolves. The mix was Extremely viscous and difficult to mix under the working conditions used. To avoid premature gelling no higher temperature was applied to the system. Connect- ' Finally, 10 g of styrene and 0.005 g of benzoyl peroxide were added to the system

given and everything gently stirred. However, the system was very viacos and contained numerous bubbles. The mixture was poured into an ingot and then heated to 120 ° for 6 hours and then to 200 ° for a further 6 hours. A similar, resinous, opaque product with numerous bubbles was obtained, which had a Barcol-ik.rte about 4U-45 and a heat resistance of 108. In contrast, the resin obtained in Example 33 after curing similar to / in Example 67 had a heat resistance of 215 °.
Example 67

200 g of bis (4-oxyphenyl) -2,2-propane liilycidyl diets : i.it a ... zpoxy equivalent weight of 191 »59 g maleic anhydride and 5 e 1, 1, 1-trin.ethylolpropane were used in a reaction. Gegecen and then 51 g of styrene and 0.05 g of benzoyl peroxide added. After the mixture obtained was stirred, it was poured into various ingot shapes. The curing was as follows: 2 hours at 5u °; 1 hour at 80 °; 60 hours at 120 ° and ν 6 studies at 200. So y / urde a narcotic product with a

009813 / 16U

BATH

atd 1 B e at 260 ° 1 ° / o weight loss 68 1 O _ 26th 2.9 49 3.7 20th 92 8.0 i a P i ei

- 57 Barool hardness of 52 and. obtained a heat resistance of 70 °.

Then the bars were heated for different times and the weight loss was calculated ^{in ϋ} / ο at certain intervals. The results were as follows:

Table 16 Heat resistance; ⁰ C.

70 200 145 163 the bars broke

Bis- (3 »4-epoxycyclohe / xylmethyl) -fu / marate, maleic anhydride, 1,2,5-hexanetriol and iriallyl cyanurate were mixed in such an amount that 1.0 carboxyl groups of the LIaleinst-ureanhydrid and Ο ,? Hydroxyl groups of the 1,2,6-hexanetriol pr. Epoxy group of Bi3 - (; 5,4-epoxycyclohexylmethyl) -funiarates and = * && 1.0 äthyleniscne groups of triallylcyanurates per ethylenic group of iv.aleic anhydride and bis (3,4-epoxycyclohexylmethyl) -iu-marate were present. The mixture obtained was heated to about 120 ° for about 4 hours and to 10 ° for a further 6 hours, and a hard, tough resin was thus obtained.
Example .69

Bis- ( 3 , 4-epoxy-6-methylcyclohexyli.iethyl) maleate, succinic acid amydride, glycerol and diallyl phthalate were mixed in such complexes that 0, o carboxyl groups of succinic anhydride and 0.4 hydroxyl groups of glycerol per epoxy group of Biü - (^ , 4-epox _[ / -6-meth _t / lcyclohexylmethyl) maleate and ^ v ^ ä 0.6 utJiylenisohe groups de3 diallyl phthalate per ethylenic group of the Biü- (3,4-epoxy-6-mebhylcyclohexylmethyl) maleate. Then 0.1 wt. Fo benzoyl peroxide, based on daa

009 8 1 3 / 16U

bad of.:g;:\'al

Total weight of the preparation, added and the resulting mixture heated for about 6 hours at about 120 ° and a further 6 hours at 160 °. A hard, solid resin was thus obtained. Example 70

Bis- (3,4-epoxy-ö-methylcyclohexyl-ethyl) -maleate, adipic acid, glycerol and diallylphthalate were mixed in such a way that the carboxyl groups of the AdipindLure and U, ο hydroxyl groups of the glycerol per iipoxy group deu Bia - (3,4-epoxy-C -... ei; ^, / lcyclohexylmethyl) -iiialeates and wj * 0.6 Etnyleu group :! of diallyl phthalate per ethylenic group of xJij- (i, 4-e _i , oxy-6-riietn / lcyclohexylir-etiiyl) -i: .ü, ledtes. Then υ, 'Ι Ge, / .-; ^; . o benzoyl peroxide, uezogen the Gedanitge '/ ICNT of l ^J rdi; arates added uni iüioehung the resultant about 6 otandexj. on et.va i2ü ° and further δ hours = * ---_ ■ loO orl'iitzc. In this way a generally solid resin was obtained.
Example 71

Bis- ( 5 , 4-epoXj-o-iiiä: i _v ^r lc
3t.ureanlvdrid, Eti-ylen ^ lykol ;.: AL
Mixed quantities, last 0, ^. Garboxylgrapce-i des Phti.al3äurear-hy; lrid3 and 0.4 hydroxyl groups of the ethylene glycol per epoxy group of the bis- ( 3, 4-epoxy-b-methylcyclohexyl-et. Yl) -iaaleatea and v ^ ft 0.5 ethylenic Groups of Diallylphthalat es pro ätnyleni scher Gruijpe des Bia-C ^^ - epoxy-j-methylcycloiiexylxiiet yl) -ualeates vorlagen. Then 0.1 Gev /.-/3 benzoyl peroxide, based on the total weight of the preparation, was added and the resulting liquid was heated to about 120 ° for about 6 hours and then to 160 ° for another 6 hours. A hard, solid resin was thus obtained.

009813 / 16U

Example 72

Bis- (3> 4-epoxycyclohexylnetyl) -fumarate, tetrahydro-] tafhalic acid, ihydride, 1,2,6-hexanetriol and triall / cyanurate were mixed in such helmets that 1.0 carboxyl groups of the tetrahydrophthalic anhydride and 0, b Hydroxyl groups of the 1, £ i, 6-hexanetriol per epoxy group of the bis (3,4-epoxycycloi: exyl:.: Ethyl) fumarate and 1.0 ethylenic groups of the triallyl cyanurate per ethylene group of the tetrahydrocycloid anhydride and dea bio- (3,4 ~ epoxycyclohexyl-ethyl) - ± 'umarate3 templates. The mixture obtained was heated for about 4 hours at 120 ° and for a further 8 hours at 180 °. A hard, tough resin was thus obtained.
Example 73

Bis- (3 ^ -epoxycyclohexyl.-r-ethyl) -i'uuiarat, Itaconaäureaniiydrid, 1, 2,6-hexanetriol and triallylcya.iurate were converted into such ^ lie, jei..ish, last. 1, ^ Oaroox ^ lruppen of itaconic anhydride and 0.5 Hydroxylgrαρι en des 1, ^, o-Hexanetriolts per Epoxy group of bis (3,4-epoxycyclur: exyl: .. ethyl) ~ fu: .. arates and * © »· 1.0 ethylenic group of the triallyl cyanurate per ethylenic group Itaconic anhydride and egg (3,4-epoxycyclohexylmethyl) -fua.arate group templates. The resulting mixture was about 4 hours at about 120 ° and a further c hours at 180 ° heated. A hard, tough resin was obtained in this way.

009813/18 U

Claims (22)

Claims Holding curable, polymerisable preparation, consisting of (a) a polyepoxide containing at least one, to adjacent cycloaliphatic carbon atoms bound oxirane oxygen atom ent _T ', (b) a Polycarbonsäureverbiiidung and (c) a monomeric ethylenically unsaturated compound which in addition to the - 1 » Polyethylene ethylene groups do not contain any functional groups which are reactive with neighboring K ρ oxy groups or carboxyl groups; with the prerequisite that in addition to the monomeric, othylenically unsaturated compound, at least one component, at least one ethylenic group, which is associated with the monomeric, ethylenically unsaturated compound is polymerizable, contains, in such relative amounts that 0.16-5.0 carboxyl groups of the acid compound per epoxy group of the polyepoxide and 0.002-5.0 ätnyleniücne groups of the monomeric, äthyleniacja unsaturated Compound per ätnylehiucaer group of the other components are present. 2.- A preparation according to claim 1, characterized in that the Polycarboxylic acid compound is a polycarboxylic acid anhydride or a polycarboxylic acid. 3. ~ Pr ^ p-irat according to claim 2, dadurc / χ characterized that the Anhydride or the acid is an ethylenically unsaturated polycarboxylic acid anhydride or an ethylenically unsaturated polycarboxylic acid is. 4.- Preparation naci. Anapruch 1-3, dadurcr. gekerüizeichnet that the polyepoxide is a liepoxyd, in which at least one oxirane ä for t off it atom of Ce-iacnbarte cycloaliphatic carbon atoms gebunden.ist. 0 0 9 8 1 3/1 6 U 5.- preparation according to claim 1-4 »characterized in that the relative amounts of the components 0k33-4.0 carboxyl groups Acid bond per epoxy group of the polyepoxide and 0.2-2.0 ethylene Groups of the monomeric, ethylenically unsaturated compounds bond per ethylenic group of the other components aahaiifeift. 6.- preparation according to claim 1-5 »characterized in that it e.Lii contains polyol in an amount such that up to 2.0 hydroxyl groups of the polyol are present per epoxy group of the polyepoxide. 7 · - preparation according to claims 1-6, characterized in that the monomeric, ethylenically unsaturated compound besides the polymerizable Ethylenic groups do not have functional groups with adjacent epoxy groups, carboxyl groups, and hydroxyl groups are reactive contains. 8.- preparation according to claim 6 and 7, characterized in that the polyol is present at such a level that 0.16-2.0 Hydroxyl groups of the polyol are present per epoxy group of the polyepoxide. 9.- preparation according to claim l-ö, characterized in that the Polye ^ ü ^ yd is a diepoxide in which both oxirane oxygen atoms individually to neighboring cycloaliphatic carbon laboratories are bound. 10.- preparation according to claims 1-9 »characterized in that the Polyepoxide, dicyclopentadiene dioxide, 4-vinylcyclonexane dioxide, 3,4-epoxy-G-methylcyclohexyliuethyl-j ^ -epoxy-δ-methylcyclohexane carboxylate or βia (2, ^ - epoxycyclopentyl) ether. 00 9 8 1 ^{3/1 6 U ßAD} - o2 - 11.- Preparation according to claim. ' 1-1 υ, countersigned by the fact that the Ethylene unsaturated acid compound is lilaleinic anhydride. 12.- Preparation according to spoke 1-11, characterized by the fact that the: .iono;., Ore, äthyleniac- '. Ldi _; , 3satti.i, th compound "styrene i. ^ C. 13 · - preparation naci. Claims 1-12, characterized thereby, Ia ₁ . the polyol is an aliphatic polyhydric alcohol. 14 · - Preparation according to Ansr; ruch 1-13 »dadurcn ^ eke: aizeici: net, daw daa Pol / ol is 1,1,1-TriuGtnylolpropane. 15.- Process for the production of synthetic resins, because it indicates that at least (a) one polyepoxide, e the at least one cycloaliphatic carbon dioxide ... The polycarbonate compound and (c) a monomeric, ethyleniacii unä'esLvtti ^ te compound which, apart from the poly-erioable ethylenic groups, contains small functional groups which are reactive with neighboring epoxy groups and caroxyl groups, πι π provided that in addition to the monomeric, ätnyleni3cn unsaturated compound Liindestens one of unreacted ϊίοι: ^ s orient at least one ethylenic, ait the Cono:; ng, Ltnyleniac ;: _un;. ss; saturated-i compound ρolyineriubaren group enti.Llt, in solciier. relative proportions, since 0.16-5.0 carboxyl group: the .jfc.ureverbi.dur per epoxy group of the polyepoxide and 0.002-5.0 ethyleneidcns groups of the monomeric, ethylene-based groups. The unsaturated carbonization of the ethylene group of the other components is present in the presence of a catalyst with free radicals, converted at a temperature of 15-275, until a hard, identical resin is formed. 0 0 9 8 1 3/1 6 U 16.- Procedure nao.i claim. 15i is characterized by ^ that as Acid compound is a polycarboxylic anhydride or a polycarbonic acid is used. 17, - Method according to claims 15 and 16, characterized by this, dafc an ethylenically unsaturated carboxylic acid anhydride as the acid compound or an äthylenisci; uii, unsaturated dicartic acid used will. 1ü, - procedure according to claims 15-17, dadurc. characterized- that in the Reaktioi-is: .. isci: uüg ei .. polyol in such a small amount is useful if there are up to H ₁ O hydroxyl groups of the 3 polyol per epoxy group of the polyepoxide. 19.- The method according to claim 15-U-, characterized in that dab alj tolyepoxide a saturated liex oxide is used. 20.- Method according to Anjprucn 15-19 _f, characterized in that maleic anhydride is used as the rolycarbonate acid compound. 21.- Method according to claim :. 1p-2o, dadui-ci. .-eiienr ^ zeiciinet, duü as:;: onc: .. ere, ethylenic urigeaüttierte compound styrene used will. 22.- Procedure after Claim 1 ^ -21, characterized in that as tolyol 1, 1, i-'lriinethylolprppan is ver.vied. 23 · - method according to claims 15-22, dadurc. gekeianzeichnet that ί as a polyepoxide, 4 £] ox _{v-ö-i..ethylcycloiiexyl:.} .. ethyl-3 '4-3Loxy-6-inethylcycloliexar-carbcxylat, Licyclope.-itadiendioxyd, 4-Vinylcyclohexei.dioxyd or Bio - (2, i-eioxycyclcpen ^ yi) -ether is grazed. The? A "tentar..valt: 009813 / 16U ^l * BATH ORIGINAL