DE2113884A1 - Hardenable mixtures of epoxy resins and piperidine derivatives - Google Patents

Description

CIBA-GEIGY AG, BASEL (SWITZERLAND)

Case 6998 / E

β Munich 2, ßräühouistraße 4 / H |

Curable mixtures of epoxy resins and piperidine derivatives.

The present invention relates to curable mixtures which are used for the production of moldings, impregnations and coatings and bonds are suitable and which are characterized in that they (a) a polyepoxy compound with average more than one epoxy group in the molecule and (b) a substituted ^ -amino-O-aminomethyl-piperidine as hardener general formula.

109842/1833

CH
'VcB ₈ - *. (X)

CH ₂ CH ₂

where R is an alkyl, alkenyl , cycloalkyl, cycloalkenyl, aralkyl or aryl radical containing preferably 1 to 7 carbon atoms, in particular a lower alkyl radical having 1 to 4 carbon atoms.

Some compounds of the formula (I) are described in the literature , for example l-methyl-4-amino-3-aniinoraethyl-piperidine [J. Colonge, G. Descates, G. Fresnay, Compt.Rend. 256, 2638-9
(19β5)) 3 which is prepared by reducing l-methyl - ^ - amino-3-cyano tetrahydropyridine by means of sodium in alcohol
could be.

Their use as hardeners for epoxy resins , however, has not been mentioned anywhere in the literature or suggested to the person skilled in the art.

In general, the compounds of formula (I) can be conveniently prepared by adding substituted ^ -Απι1ηο-3-cyano- 1,2,5,6-tetrahydropyridines of the formula

'f a c

CH ₂ Χ? - C = kN . (II)

W.
1 0 9 8 ^R A 2/1 8 3 3

wherein R has the same meaning as in formula (I) in an known way hydrogenated.

The hydrogenation is preferably carried out in the presence of a catalyst.

The hydrogenation catalysts are Raney nickel or Raney cobalt particularly effective. You can also use a cobalt oxide catalyst on a suitable support material that reduced in the hydrogen stream to cobalt metal catalyst.

As hydrogenation catalysts are also catalysts based on platinum and palladium in question, which as platinum or Palladium black, as colloidal platinum or palladium, or as platinum or palladium oxide or hydroxide catalysts can be used.

The usual support materials are used for such catalysts Materials such as asbestos, pumice stone, kieselguhr, silica gel, silica, activated carbon, the sulfates, carbonates or oxides of the Metals of groups II to VIII of the periodic table, in particular magnesium, calcium, barium, zinc, aluminum, Iron, chromium and zirconium, in question.

The hydrogenation can be carried out without pressure using the methods customary in the laboratory and in technology, e.g. in the shaking duck, as well as under pressure in the autoclave.

109842/18 33

Solvents which can be used in the hydrogenation are those customarily used together with the above-mentioned types of catalyst organic solvents, preferably lower aliphatic Alcohols such as methanol or ethanol are used.

The catalytic reduction is usually carried out by the suspension or solution of the 4-amino-J5-cyano-1,2,5,6-tetrahydropyridine mixed with the catalyst and introducing hydrogen gas into the reaction mixture. The hydrogenation can in principle at atmospheric pressure and room temperature

clocks, but elevated pressures of 50 atmospheres are preferred and above as well as increased reaction temperatures in the range from 50 to 150 C. The hydrogenation is continued as long as until no more hydrogen is absorbed. After the hydrogenation is complete, the catalyst is removed, for example, by filtration separated off and the solvent was distilled off.

The hydrogenation can also be carried out by other known methods, for example by treatment with alkali metals such as metallic Sodium, perform in alcoholic solution.

The substituted 4-amino-> cyano-1,2,5,6-tetrahydropyridines used as starting materials can by cyclizing bis-cyanoethylated amines of the formula

^ ₂₂
RN. (III)

can be obtained, wherein R has the same meaning as in formula (I). 109842/1833

To prepare the curable mixtures, it is expedient to use epoxy groups of the polyepoxy compound per 1 equivalent (a) 0.5 to 1.3 equivalents, preferably about 1.0 Equivalent, nitrogen-bonded active hydrogen atoms of the substituted ^ -amino-J-aminomethylpiperidine of Formula (i).

Particularly suitable polyepoxide compounds (a) are those with an average of more than one glycidyl group, β-methylglycidyl group or 2,3-epoxycyclopentyl group bonded to a heteroatom (eg sulfur, preferably oxygen or nitrogen); Mention may be made in particular of bis (2,3-epoxycyclopentyl) ethers; Di- or polyglycidyl ethers of polyhydric aliphatic alcohols, such as 1,4-butanediol, or polyalkylene glycols, such as polypropylene glycols; di- or polyglycidyl ethers of cycloaliphatic polyols, such as 2,2-bis- (4 ^! -Hydroxycyclohexyl) propane; di- or Polyglycidyl ethers of polyhydric phenols, such as resorcinol, bis (p-hyaroxyphenyl) methane, 2,2-bis (p-hydroxyphenyl) propane (= diomathane), 2,2-bis (4'-hydroxy-3 ', 5'-dibromophenyl) propane, l, l, 2,2-tetrakis (p-hydroxyphenyl) ethane, or of condensation products of phenols with formaldehyde, such as phenol novolaks and cresol novolaks, obtained under acidic conditions; Di- or poly- (ß-niethylglycidylfather of the above-mentioned polyhydric alcohols or polyhydric phenols; polyglycidyl esters of polybasic carboxylic acids, v / ie phthalic

109842/1833

r 6 -

acid, terephthalic acid, δ-tetrahydrophthalic acid and hexahydrophthalic acids N-glycidyl derivatives of amines, amides and heterocyclic nitrogen bases, such as Ν, Ν-diglycidyl-anilln, Ν, Ν-diglycidyl-toluidine, Ν, Ν, Ν ', N'-tetraglycidyl-bisCp-anil-

nophenyl) methane; Triglycidyl isoeyanurate; Ν, Ν-diglycidyl- ■ ■ ♦

ethylene urea; N, N'-diglycidyl-5 , 5-dimethyl-hydantoin, N, N ^r -diglycidyl ~ 5 ~ isopropyl ~ hydantoin; N, N'-diglycidyl-5,5-diethyl-6-isopropyl-5,6-dihydro-uracil.

If desired, the polyepoxides can be used for * Reduce the viscosity of active thinners such as styrene oxide, butyl glycidyl ether, isooctyl glycidyl ether, phenyl glycidyl ether, Cresyl glycidyl ether, glycidj'-lester of synthetic, highly branched, mainly tertiary,

add aliphatic monocarboxylic acids ( ^IT CARDURA E ").

The Härtung'der inventive curable compositions to form shaped bodies and the like is advantageously bulky in the temperature interval from 20 to 150 ⁰ C. It is the curing in a known manner in two or more stages, to carry out, wherein the first curing stage, for example at room temperature and post-curing at a higher temperature is carried out. .-.

If desired, the hardening can also be carried out in this way

done in 2 stages by starting the curing reaction terminated prematurely, or the first stage carried out at room temperature or only slightly elevated temperature is, with a still meltable and soluble, hardenable precondensate (so-called "B-stage") from the epoxy compo-

109842 / 1833-

nente (a) and the amine hardener (b) is obtained. Such a pre-condensate can be used e.g. for the production of "prepregs", Press masses or, in particular, sinter powders are used.

To shorten the gelation and hardening times, known accelerators for amine hardening, e.g. mono- or polyphenols, such as phenol or diomethane, salicylic acid,

tertiary amines or salts of hydrofluoric acid, such as NIKSCN, can be added.

The term "hardening" as used here

means the conversion of the soluble, either liquid or meltable polyepoxides into solid, insoluble and infusible, three-dimensionally networked products or materials, usually with simultaneous' Shaping into molded bodies, such as cast bodies, pressed bodies, laminates and the like, or "flat structures" such as Coatings, lacquer films or bonds.

The curable mixtures according to the invention of polyepoxide compounds (a) and substituted ty-amino - ^ - aminomethyl-piperidine of formula (I) as hardener (b) can also be used in any phase with customary modifiers before hardening, such as extenders, fillers and reinforcing agents, pigments, dyes, organic solvents, plasticizers, leveling agents agents, thixotropic agents, flame retardants, mold release agents are added.

109842/1833

As an extender, reinforcing agent, filler and pigments that can be used in the curable mixtures according to the invention are, for example: coal tar, Bitumen, textile fibers ^, glass fibers, asbestos fibers, boron fibers, carbon fibers, cellulose, polyethylene powder ,. Polypropylene powder; Quartz flour; mineral silicates such as mica, asbestos flour, slate flour; kaolin, aluminum oxide trihydrate, Chalk flour, gypsum, antimony trioxide, bentone, silica airgel ("ASROSIL"), lithopone, barite, titanium dioxide, Soot, graphite, oxide paints such as iron oxide, or metal powder,

like aluminum powder or iron powder.

Suitable organic solvents for modifying the hardenable mixtures are e.g. toluene, xylene, n-propanol, butyl acetate, acetone, methyl ethyl ketone, diacetone alcohol Ethylene glycol ronomethyl ether, monoethyl ether and monobutyl ether.

As plasticizers for the modification of the curable mixtures, e.g. dibutyl, dioctyl and dinonyl phthalate, Tricresyl phosphate, trixylenyl phosphate, and more Polypropylene glycols are used.

As flow control agents when using the hardenable mixtures, especially in surface protection For example, you can use silicones, cellulose acetobutyrate, polyvinyl butyral, waxes, stearates etc. (some of which are also called Mold release agents are used).

10 9 8 4 2/1 833

The polypropylene compounds can also be used in a known manner, especially for use in the paint sector with "carboxylic acids, especially higher unsaturated fatty acids, be partially esterified. It is also possible to add other curable synthetic resins, e.g. phenoplasts or aminoplasts, to such lacquer resin formulations.

The curable mixtures according to the invention can be prepared in the customary manner with the aid of known mixing units (Stirrer, kneader, rollers, etc.).

The curable epoxy resin mixtures according to the invention are mainly used in the areas of surface protection, electrical engineering and lamination processes and in construction. They can be used in a formulation adapted to the specific application, in the unfilled or filled state, optionally in the form of solutions or emulsions, as paints, varnishes, as Sinter powders, molding compounds, injection molding formulations, dipping resins, casting resins, impregnating resins, binders and adhesives, as tool resins, laminating resins, sealing and leveling compounds, flooring compounds and binders for mineral Aggregates used v / earth.

In the following examples, unless stated otherwise, parts are parts by weight and percentages are percentages by weight. Parts by volume and parts by weight relate to one another like milliliters to grams »

1098 42/1833

The following epoxy resin was used for the preparation of curable mixtures described in the examples:
Epoxy resin A.

By condensation of diomethane (2,2-bis (p-hydroxyphenyl) propane) with a .stoichiometric excess of epichiorhydrin prepared in the presence of alkali, mainly from diomethane diglycidyl ether of the formula

GH ₂ CH-CH ₂

0 - CH- 0

existing polyglycidyl ether resin that is liquid at room temperature (technical product) with the following key figures:

Epoxy content: 5.1 to 5.5 epoxy equivalents / kg Viscosity (Hoeppler) at 25 ° C: 9000 to 1300 cP.

Epoxy resin B

By condensation of hydrogenated diomethane (2,2-bis- (p-hydroxycyclohexyl) propane) produced with a stoichiometric excess of epichlorohydrin in the presence of alkali, mainly from hydrogenated diomethane diglycidyl ether of the formula

109842/1833

existing diglycidyl ether resin that is liquid at room temperature (technical product) with an epoxy content of 4.46 epoxy equivalents / kg.

Epoxy resin C

Tetrahydrophthalic acid diglycidyl ester with the following key figures:

Epoxy content: 6.45 equivalents / kg Viscosity (Hoeppler) at 25 ° C: 450-550 cP

To determine the mechanical and electrical properties the moldings which can be produced from the curable mixtures described in the examples below were used to determine flexural strength, deflection, Impact resistance, and water absorption panels of 135 x 135 x 4 mm manufactured. The test specimens (βθ χ 10 χ 4 mm) for the determination the water absorption and for the bending and impact bending test (VSM 77103 or VSM 77IO5) were worked out of the plates.

109842/1833

The substituted 4-amino ~ 3-aminomethyl-piperidines used as hardeners in the following examples appear as is made as follows:

Example A.

Production of l-methyl - ^ - amino - ^ - aminomethyl-piperidine (J. Colonge, G. Descates, G. Fresnay; Compt.Rend, 256 , 2638-9 [19633)

a) 150 g of recrystallized and well dried 1-methyl-4-amino-3-cyano-1,2j 5-i 6-tetrahydropyridine are suspended in 500 ml of methanol and in a shaking autoclave with Raney nickel, activated with 2 % Palladium, hydrogenated at 100 ° C and about 100 atmospheres H. Hp uptake ends after 5 hours. The catalyst is filtered off and the methanol is removed on a rotary evaporator (bath temperature not above 30 ° C.). The residue is fractionated over a 40 cm packed column

Yield: 57.9 g)

Boiling point 112-19 C / 12 mm Hg (in the literature J. Colonge et al. 74 ° C / 0.5 mm Hg)

A fraction at a boiling point of 116-17 ° C. / 12 mm Hg was taken for the analysis.

Analysis: C ₇ H ₁₇ N ₅ (M = 143.23)

Calculated: C 58.70 H 11.96 N 29.33 Found C 52.56 H li _r 66 N 29.57.

1 0 9 8 U? I 1 · "■ 3

The mass spectrum does not reveal the molecular peak at - Instead, a fragment occurs at - 126 that passes through

ti

NH-2 cleavage occurred. A main fragment has the mass - J50 and corresponds to CII ₂ Ü

The NMR spectrum in CCl ^ is very complex. You can see them N-CIU group at 2.15 5 and 4 NH protons at 1.055.

IR spectrum:

Band [cm "] · Interpretation

m. stretching vibration NH _p

m. stretching vibration NH _? and NH

I6IO st. "Deformation vibration

b) 96 g (0.7 mol) of l-methyl-4-amino-3-cyano-l, 2,5,6-tetrahydropyridine are in a solution of 100 g of ammonia in 300 ml of ethanol in an autoclave at 125 ° C and Hydrogenated 100 atmospheres in the presence of 10 g of Raney nickel within 4 hours. The catalyst is filtered off, the piltrate is concentrated on a rotary evaporator and the residue is first distilled in vacuo without a column. 75.4 g of crude amine with a boiling point of 30-110 ° C./10 mm Hg are obtained , 4 g (66.3%) of 1-meth / 1-4-amino-3 ~ orninornethyl-piper'idin of boiling point 107-LO-I ⁰ O / 9 mm Hg.

109842/1833 BAD

2113384

Analysis: C ₇ H ₁₇ M ₅ (M - 1 ^ 3.23)

Calculated: C 58.70 H 11.96 M 29.33 Found: C 58.56 H 11.66 M 29.57.

The mass spectrum does not give the molecular peak at -

Instead, a fragment appears at - 126 that passes through ΝΗ ^, - split arose. The Piasse ~ has a main fragment

** ' ■ G

and corresponds to CH ₀ = Μ * ΙΗ _Ο .

el cw

The NMR spectrum in CCl ₂ is very complex. One recognizes the) N-CH, group at 2.15 $ and 4 NH protons at 1.055.

IR spectrum:

Band [cnT] - interpretation

3380 m. "_ ■ -." "· Stretching vibration iHf

33ΟΟ m, '' - '' "Stretching vibration KH ^ and NIi

I6IO st. . . - ■ "." .- Deformation vibration

1-Methyl-4-aminopiperidine can be used as by-products in the forerun and detect the 1,3-dimethyl-4-amine-piperidine.

Example B. Preparation of 1-n-butyl-4-amino-3-aminomethyl-piperidine

Stage 1: Dissolve 1.5 g of sodium in 300 ml of tert-butanol and added dropwise with stirring. 50 C within 2 hours 81, 4 g N, H-bis- (ß-cyan:> aeth.yl) -n-butylamLn to. Then stops

10 9 8 4 2/1833

the solution is left to stand at room temperature for 3 hours at 50 ° C., and the solution is then concentrated on a rotary evaporator. The residue is recrystallized from 100 ml of toluene. After suctioning off and washing with a little toluene, the crystals are dried at 40 ° C. in vacuo. Yield: 36.9 g (45.4 fo) of in -butyl-4-araino-3-cyano-1,2,5,6-tetralihydropyridine with a melting point of 69.5-70.5 ° C. The filtrate is concentrated and the residue was recrystallized from 30 ml of toluene and 60 ral petroleum ether. A further 21.5 g with a melting point of 69-70.5 ° C. are obtained, so that the overall yield increases to 5.5 g (71.8 %) . Analysis: C ₁₀ H ₁₇ N ₃ (M = 179.27)

Calculated: C 67.01 H 23.44 Found: C 67.18 H 23.65

Stage II: 85.5 g of the 1-n-butyl-4-amino-3-cyano-l, 2,5,6-tetrahydropyridn produced in the 1st stage are dissolved in 250 ml of ethanol and 80 g of ammonia in an autoclave at 110.degree and 100 atmospheres, in the presence of 10 g of Raney nickel, hydrogenated within 4 hours. The catalyst is filtered off with suction, the hydrogenation mixture is initially distilled without a column and 66.8 g of bp 80-141 ° C. are obtained. Fractional distillation over a spinning band column gives 59 * 0 g (67.0 %) of in -butyl-4-amino -3-arainomethy1-piperidine, boiling point 136-138 C / 9 mm Hg. Analysis: C ₃₀ H ₂₅ N ₃ (M- 185.31)

Calculated: C 6'l, 8l, H 12.51, N 22.67 Found: C 64.83 H 12.50 21 22.84

1098Ä7 / 1R33

1-n-Butyl-4-aminopiperidine is obtained as a by-product from the forerun.

Example C:

Preparation of l-isopropyl-4-amino-5-aminomethyl-piperidine

Stage 1: 1.0 g of sodium is dissolved in 200 ml of tert-butanol, 84 g of N, N-bis (ß-cyanoaethyl) isopropylamine are then added all at once at 60.degree. C., and the mixture is then heated to 60.degree. C. for 6 hours It is concentrated on a rotary evaporator and the residue is recrystallized from 100 ml of toluene. After suctioning off and washing with cyclohexane _{/ to} which a little benzene has been added, the crystals are dried at 50 ° C. in vacuo. Yield: 57.5 g of 1-isopropyl-4-amino-5-cyano-1,2,5i6-tetrahydropyridine; Melting point 8o C.

Concentration and recrystallization from 60 ml of cyclohexane give a further 6.1 g of melting point 79-80 C. Total yield: 63.4 g (75.5 %) from the pellet.

For the analysis, 2.0 g of the substance obtained were recrystallized from 5 ml of toluene.
Yield: 690 mg; Melting point: 79.5-80 ° C. Analysis: CJH ₁₅ N, (M = ^165.24):: ..

Calculated: C 65.42 H 9.15 N 25.4 ^ Found: G 65.82 H 9.00 N 25.17

Stage II: 91 g of the l-isopropyl-4-amino-j5-cyano-1,2,5> 6-tetrahydropyridine prepared in stage I are in JOO ml of ethanol and 100 g of ammonia in the presence of 10 g of Raney nickel at 125 ° C and a pressure of 100 atmospheres

1098A2 / 1833

hydrogenated in the autoclave within 2 hours, the catalyst is filtered off and the solution is concentrated on a rotary evaporator. Distillation of the residue, without a column, in vacuo gives 78.9 g of crude amine with a boiling point of 110-210 ° C./9 mm Hg. Fractional distillation over a spinning band column gives 67.9 g (72.1 %) of 1-isopropyl-4 ~ amino-3-aminomethylpiperidine boiling point 130 ° C / 10 mm Hg.

Analysis: ^c q ^H 2i ^N 3 ( ^{M =} ! 7 ¹ ^ ² 9)

Calculated: C 63.11 H 12.56 N 24.53 Found: C 65.12 H 12.44 N 24.78

Example D Preparation of l-cyclohexyl-4-amino-3-aminomethyl-piperidine

Step 1: Dissolve 500 mg of sodium in 100 ml of tert-butanol, dropwise under stirring at 4O ⁰ C. 50 g N, N-bis (.beta.-cyanoethyl) -cyclohexylamine within 1/2 hours, then heated for 12 hours at 60 ° C; crystals separate out in the process. After standing for two days at room temperature, the crystal slurry is filtered off with suction, washed with cyclohexane and dried at 50 ° C. in vacuo.

Yield: 34.8 g of 1-cyclohexyl-4-amino-3-cyano-1,2,5 * 6-tetrahydropyridine; Melting point 128-129 ⁰ C. From the obtained Piltrat further 5 * 5 g of melting point 125-127 ^O C.

Overall yield: 40.3 g (80.8 %).

For the analysis, 1.0 g of the substance obtained was recrystallized from 10 ml of cyclohexane.

109842/1833

" ^l8 " 2113384

Yield: 520 mg; Melting point 128.5-129 ° C. Analysis: C ₁₂ H ₁₉ N ₅ (M = 205.31)

Calculated: C 70.20 H 9.33 N 20.47 Found: C 70.33 H 9.29 N 20 * 37

Stage II: 13 ² I-, 8 g of the 1-cyclohexyl-4-amino-3-cyano-l, 2,5,6-tetrahydropyridine obtained in the 1st stage are dissolved in 3OO ml of ethanol and 100 g of ammonia with 7 g Raney-Niekel hydrogenated at 110-115 ° C. and a pressure of 100 atmospheres in an autoclave. After the catalyst and the solvent have been removed, it is first distilled in vacuo without a column; wherein one 116.6 g of crude amine having a boiling point receives 170-200 ⁰ C / 10 mm Hg. Fractional distillation over a spinning band column gives 104.7 g (75.5 %) of l-cyclohexyl- ^ - amino-jS-aminometnyl-piperidine with a boiling point of 174 C / mm Hg. The l-cyclohexyl-4-amino can be used in the forerun -piperidine detect.
Analysis: C ₁₂ H ₃₅ N ₃ (M = 211.35)

Calculated: C 68.20 H 11.92 N 19.88

Found: C 68.43 H 11.97 N 19.79 The mass spectrum agrees with the formula given.

Example E. Preparation of l-benzyl-4-amino-3-aminomethyl-piperidine

107.5 g of 1-benzyl-4-amino-3-cyano-1,2,5,6-tetrahydropyridine [prepared according to Taylor, Tetrahedron 2 ^, 885 (1967)] in 300 ml of ethanol and 100 g of ammonia with 10 g of Raney nickel

109842/1833

hydrogenated at 115-120 C and 100 atmospheres in an autoclave. After the catalyst and the solvent have been removed, distillation is carried out in vacuo without a column.

Yield: 82.7 g of crude amine with a boiling point of 115-160 ° C. / 0.3 mm Hg. Fractional distillation over a spinning band column gives 76.8 g ($ 69.5) of l-benzyl - ^ - amino-J-aminomethylpiperidine from Boiling point 190-192 ° C / 10 mm H. Analysis: C ₁₃ H ₂₁ N ₅ (M = 219.33) Calculated: C 71.19 H 9.65 N 19.16 Found: C 70.68 H 9, 68 N 19.15

109842/1833

Application examples example 1

a) 66 parts of epoxy resin A and 12.5 parts of 1-methyl-4-amino-J-aminomethyl-piperidine (corresponding to a ratio of epoxy equivalent: active nitrogen bound H atoms = 1.0: 1.0) were at room temperature (25 C) mixed, degassed in a vacuum and in aluminum

cast molds. The mixture gelled with an exotherm Warming. After cooling, the material was post-cured at 100 ° C for a further 24 hours.

The cast bodies obtained had the following properties:

Flexural strength according to VSM 771Ö3 = 15.1 kg / rrim ² deflection according to VSM 771OJ5 = 11.5 mm

Impact resistance according to P

VSM 77IO5 = 47 cmkg / cm

Water absorption (24 hours, 20 ° C) = 0.11 % glass transition temperature,

measured with DSC 1 *) = Ho, ° C

W *) Differential Scanning Calorimeter (according to Perkin-Elmer)

b) By pouring the curable mixture described under a) into molds preheated to 40 C with the dimensions Ι4θχΐ4θχ4 mm and curing for 4 hours at 80 ° C. and 12 hours at 14 ° C., castings with the following properties were obtained:

109847/18 3 3

Flexural Strength = 14.5 kg / mm

Deflection = l4 mm

Impact resistance = 18 cmkg / cm

Heat resistance ·.

according to ISO R 75 = 87 ⁰ C

Example 2 · ·.

35.7 parts of 1 -'-methyl-4-amino-3-aminomethyl-piperidine and 224 parts of epoxy resin B were mixed and processed further as in Example 1 b).

The moldings obtained had the following properties: dimensional stability according to DIN 53461 92 ° C. flexural strength according to VSM 77103 7.5 kg / mm ² deflection according to VSM 77103 5.8 mm

Impact strength according to VSM 77105 10.6 cmkg / cm Glass transition temperature * 107 C

* measured in the differential scanning calorimeter (DSC-l) with a heating rate of 16 ° C / min.

Example 3

35.7 parts of 1-methyl-4-amino-3-aminomethyl-piperidine and 155 parts of epoxy resin C were mixed and processed further as in Example 1 b).
The moldings obtained had the following properties:

1Ö9842 / 1833

2113884 I. O
kg / mm 97 ° c mm 9.2 ρ
emkg / cm 2.9 ο
kg / mm 9.6 7.1 C. 10.0 113 °

Dimensional stability according to DIN 53461, bending strength according to VSM 77103 deflection according to VSM 77103 Impact strength according to VSM 77105 tensile strength according to VSM 77101 elongation at break according to VSM 77101 Glass transition temperature (DSC-I) '

Example 4

42.8 parts of 1-isopropyl-4-amino-3-aroinomethyl-p ± peridine

and 185 parts of epoxy resin A were mixed and as in Example 1 b) processed further.

The moldings obtained had the following properties: Dimensional stability according to DIN 53461 154 ° C

Flexural strength according to VSM 77103 14.4 kg / mm ²

Deflection according to VSM 77103 11.8 mm

Impact strength according to VSM 77105 37.0 emkg / cm Tensile strength according to VSM 77IOI 8.9 kg / mm ²

Elongation at break according to VSM 77IOI 11.3 %

Glass transition temperature (DSC-I) 163 ⁰ C V / water absorption (1 day; 2O ⁰ C) 0.19 %

Example 5

46.2 parts of 1-n-butyl-4-amino-3-arainomethyl-piperidine and 185 parts of epoxy resin A were mixed and processed further as in Example 1 b).

1098A2 / 1833

The moldings obtained had the following properties: dimensional stability according to DIN 55461 125 ° C. flexural strength according to VSM 77105 15.0 kg / mm ²

Deflection according to VSM 77105 14.1 mm

Impact strength according to VSM 77105 59.0 cmkg / cm

Tensile strength according to VSM 77101 7.5 kg / mm ²

Elongation at break according to VSM 77101 9.0 %

Glass transition temperature (DSC-1) 142 C

Water absorption (1 day; 20 ° C) 0.21 %

Example 5

52.7 parts of 1-cyelohexyl-4-amino-5-aminomethyl-piperidine and 185 parts of epoxy resin A were mixed and as in
Example 1 b) processed further.
The moldings obtained had the following properties:

Dimensional stability according to DIN 55461 ⁰

Flexural strength according to VSM 77105 14.9 kg / mm ²

Deflection according to VSM 77105 11.6 mm

Impact strength according to VSM 77105 51.0 cmkg / cm ²

Tensile strength according to VSM 77101 7.1 kg / mm ²

Elongation at break according to VSM 77101 8.7 %

Glass transition temperature (DSC-I) l66 ° C

Water absorption (1 day; 20 ⁰ C) 0

Example 7

54.7 parts of 1-benzyl-4-amino-5-aminomethyl-piperidine and 185 parts of Epoxy Resin A were mixed and as in

1 0 9 8 U 2 I 1 P 3 3

Example Ib) processed further.

The moldings obtained had the following properties:

Dimensional stability according to DIN 53461 Flexural strength according to VSM 77103 Deflection according to VSM 77103 Impact flexural strength according to VSM 77105 Tensile strength according to VSM 77IOI elongation at break according to VSM 77IOI Glass transition temperature (DSC-I)

Water uptake (1 day; 2O ⁰ C) 0.17

146 ° C. kg / mm C. 14.6 mm 12.2 cmkg / cm 41.0 kg / mm 8.6 % 10.4 156 °

1 Q 9 8 Λ? / 1 ^ ■■ '

Claims (1)

Claims C (l) Curable mixtures which are suitable for the production of moldings, impregnations, coatings and bonds, characterized in that they are (a) a polyepoxide compound with on average more than one epoxide group in the molecule and (b) a substituted 4-amino as hardener -j5-aminomethyl-piperidine of the general formula H _A HC - CH ₂ -NH ₂ . (I) CH ₀ contain, in which R is preferably 1 to 7 carbon atoms containing alkyl, alkenyl, cycloalkyl, cycloalkenyl, Aralkyl or aryl radical, in particular a lower alkyl radical having 1 to 4 carbon atoms. 2. Mixtures according to claim 1, characterized in that that they contain l-methyl-4-amino-3-aminomethyl-piperidine as hardener (b). 35. Mixtures according to claim 1, characterized in that they contain l-n-butyl-4-amino-3-aminomethyl-piperidine included as hardener (b). 4. Mixtures according to claim 1, characterized thereby records that they are l-isopropyl-4-amino-3-aminomethyX-piperidine included as hardener (b). 5. Mixtures according to claim 1, characterized in that that they are 1-cyclohexyl-4-amino-j5-aminomethy 1-piperidine included as hardener (b). 5. A mixture according to claim 1, characterized gekennzeichne tj it that 1-benzyl-4-amino-J- aminomethyl thy! -Piperidine included as a curing agent (b). 7. Mixtures according to claims 1 to 6, characterized in that they have epoxy groups per 1 equivalent of the po ^ epoxy compound (a) 0.5 Ms 1.3, preferably approx. 1.0 equivalent, active hydrogen atoms bound to nitrogen of the substituted 4-amino-3-aminomethylpiperidine (b) contain. 8. Mixtures according to claims 1 to _3, characterized in that they contain a polyepoxy compound (a) with on average more than one glycidyl group, ß-methylglycidyl group or 2,3-spoxycyclopenfyl group bonded to a heteroatom in the molecule. 9. Mixtures according to patent claims 1 , characterized in that they contain a polyglycidyl ether of a polyhydric phenol as the polyepox compound (a). 109842/1833 10. Mixtures according to claim 9, characterized in that that the polyepoxide compound (a) is a polyglycidyl ether of 2,2-bis- (p-hydroxyphenyl) propane contain. 11. Mixtures according to claims 1 to 8, thereby characterized in that it is used as a polyepoxide compound (a) contain a polyglyeidyl ether of a cycloaliphatic polyol. ". 12. ' Mixtures according to claim 11, characterized in that that as the polyepoxide compound (a) it is a polyglyeidyl ether of 2,2-bis- (p-hydroxycyclohexyl) propane contain. 13. Mixtures according to claims 1 to 8, thereby . * ■ · ■ - indicates that they are a polyepoxide compound (a) Contain polyglyeidyl ester of a polycarboxylic acid. 14. Mixtures according to claim I3, characterized in that that they are the polyepoxide compound (a) 4th
Diglyeidyl ester of Δ -tetrahydrophthalic acid or hexahydrophthalic acid contain. 15. A process for the production of hardened moldings, characterized in that a hardenable mixture according to claims 1 to 14 is hardened at temperatures of 20 to 150 ° C with shaping.