CS225437B1 - Amine hardening agent for solutions of epoxide resins in unsaturated monomers - Google Patents

Description

225 437

The present invention relates to amine hardeners capable of curing, in the presence of organic peroxides, solutions of epoxy resins in unsaturated, polymerizable monomers in atavas containing no unreacted amounts.

At present, epoxy resin solutions in unsaturated monomers capable of free radical polymerization are used for the production of pouring flooring, plastics, castings, glass laminates, molding tools and the like. Amine functional compounds serve as epoxy resin hardener, and organic peroxide is used alone or in the presence of organic metal compounds IV, IV, VI to polymerize the unsaturated monomer. or VIII. groups of the periodic system, optionally in the presence of other promoters (AO No. 202446). Also known is a process using a metal accelerator in the form of a complex dissolved in polyamine (AO No. 212008), or a process whereby a salt or a coordination compound of metals I to VIII is dissolved in an epoxy resin with a monomer. groups of the periodic aystem; and a µg solution is treated with polyamine and organic peroxide

For curing in practice, it is desirable that the entire system consists of the smallest possible number of ingredients that the processor has to mix in curing at a prescribed ratio. This is accomplished by the process of AO No. 212008, wherein the free radical polymerization vehicle is dissolved in the polyamine and the _{26-26 βθ Ονον} γ dissolves in the epoxy resin. The drawback of AO No. 212008 is the limited solubility of a number of otherwise suitable metal coordination compounds in poly _[ beta _{] 4 [} beta] reep. limited stability of the resulting solution. A drawback is then the limited storage life of the epoxy resin solution containing the metal salt or coordination compound.

We have found that a stable and long-storable amine hardener can be prepared which is in the presence of an organic

225 437 peroxide cures a solution of the epoxy resin in the reactive monomer to a product containing very few unreacted products by mixing in an 80-99.7 wt. % of a polyamine having a relative molecular weight of 60-1000, containing at least three amine hydrogens per molecule and 20-0.2 wt. of water and / or the alcohol or its ester with β monocarboxylic acid will dissolve 0.01-10 wt. coordination compounds of metals I.-VIII. groups of the periodic system. The resulting solution is stable and stored at room temperature without loss of activity for at least 3 months, but usually for more than 1 year.

This amine hardener can be mixed with a solution of the epoxy resin in a reactive unsaturated monomer and an organic peroxide in any order, in portions or simultaneously. However, it must not be mixed directly with β peroxide.

Any compound having a molecular weight of 60-1000 containing more than two nitrogen atoms and more than 3 amine hydrogens such as aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, tetraethylenepentamine, hexamethylenediamine and hexamethylenediamine can be used as starting polyamines. its methyl derivatives, xylylenediamines, isophorone diamine, cyclic aliphatic diamines such as 2,2-bis (4-aminocyclohexyl) propane, bis (4-amino-3-methylcyclohexyl) methane, aromatic diamines and mixtures thereof, further modified polyamines such as alkoxylated and cyanethylated polyamines, polyaminoamides prepared from dimer fatty acids and polyamines, adducts of aliphatic, cycloaliphatic and aromatic polyamines to epoxide compounds and Mannich bases prepared from phenols, aldehyde and dialkylamine or polyamine and mixtures thereof.

Coordinating compounds of metals I to VIII can be used as accelerators for the free-radical polymerization of the unsaturated monomer. groups of the periodic system, such as metal coordination compounds with enolizable beta-diketones such as acetylacetone, 2-acetylcyclopentanone, N-methyl-3-ethoxalylpyrrolidone-2,2-hydroxymethylenecyclohexanone, ethyl acetoacetate, metallocenes such as ferrocene, chromocene, These coordination compounds can also be prepared in situ by mixing the starting polyamine, the metal salt and the complexing agent, e.g., said beta-diketones.

To ensure the solubility and stability of the coordinating compound solution in the polyamine, the addition of water and / or an alcohol or a monocarboxylic acid ester thereof, such as aliphatic,

225 437 cycloaliphatic or heterocyclic alcohols, diols, glycerol, aminoalcohols such as ethanolamine, diethanolamine and triethanolamine, ethyl acetate, ethyl acetate, enolizable ketones and diketones, etc. in an amount of 0.2 to 20 wt. mixed with a polyamine and a coordinating metal compound.

These hardeners can be used for epoxy resins dissolved in unsaturated reactive monomers. As epoxy resins, all compounds containing more than one glycidyl ether, glycidyl ester or glycidylamine group in the molecule as well as epoxidation products of unsaturated compounds containing more than one oxirane group per molecule can be used. As the unsaturated reactive monomer, for example, styrene, its alkyl or halogen derivatives, vinyl acetate, methacrylic acid esters, acrylic acid esters, maleic and fumaric esters, divinylbenzene, acrylonitrile and the like, generally containing radical polymerization inhibitors, can be used to provide storage stability. These unsaturated monomers can be combined with each other or used in admixture with monoepoxide compounds such as butyl, phenyl, cresyl, lauryl glycidyl ether and the like.

For curing in combination with the polyamine hardener according to the invention, it is necessary to use organic peroxides, preferably hydroperoxides containing an -OOH group on any organic residue, e.g. butyl hydroperoxide, alpha .alpha.-cumenyl hydroperoxide, mixed ketone peroxides and the like.

The invention is further illustrated by the following non-limiting examples.

Example 1

In 55 parts of diethylenetriamine, 3 parts of ethanol and 2 parts of water, 2 parts of cobalt (II) acetylacetonate Co (acac) g · H 2 O are dissolved at 50 ° C. A brown-red solution is formed which is stable, no turbidity or sediment is formed within 3 months, and there is no change in activity.

To cure 100 wt. parts by weight of the casting epoxy resin obtained by the alkaline condensation of diane with epichlorohydrin (epoxide content 0.317 gmol -1 in 100 g), 20 wt. parts of styrene and 13 wt. 6.2 parts by weight of bis (2-ethylhexyl) phthalate are added with stirring. parts of the amine hardener according to Examples 1 and 1 wt. part of tert-butyl hydroperoxide (70%). Gelling at 20 ° C takes 40 to 50 minutes.

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Properties of hardened resin:

tensile strength 39 MPa flexural strength 66 MPa compressive strength 177 MPa impact toughness 5 J.cm

Martens shape stability 55 ° C water absorption at 23 ° C 0.3% rel. permittivity at 50 Hz 3,8 free styrene content 0,36%

The same results are obtained with an amine hardener stored at 20 ° C for 3 months.

Example 2

To the mixture of 19.8 wt. parts by weight of an amine prepared from dimeric fatty acids C 1 and triethylenetetramine (amine number 300 mg KOH / g) and 5.5 wt. 0.5 parts by weight of m-xylylenediamine are added. parts by weight of diethanolamine and 0.2 wt. parts of copper acetylaeetonate. Upon heating to 50 ° C, a clear solution is obtained which does not change its activity for 6 months.

To cure 100 wt. 26 parts by weight of the epoxy resin mentioned in the preceding example were used. parts of the amine hardener according to Examples 2 and 1 wt. % of alpha-cumenyl hydrosulfide (70%). Gelling occurs in 45-55 minutes at 20 ° C. The cured product contains 0.6 wt. free styre nu.

Example 3

To 100 g of a solution of epoxy resin in styrene and dibutyl maleate and dibutyl phthalate consisting of 67.5 wt. % epoxy resin according to Example 1, 12.5 wt. % styrene, 10 wt. % dibutyl maleate and 10 wt. 1 g of tert-butyl hydroperoxide (90%) and 9 g of an amine hardener consisting of the components listed in the table under the designation 1 to 15 are added with stirring.

Gelling occurs in 30 to 50 minutes. The resulting hard and tough product contains the amount of free styrene listed in the table.

225 437

Number Diethylenetriamine (g) Stabilizing agent (g) Metal Compound (g) Free styrene (%) 1 8 ethanol 0,8 Cu (acac) ₂ 0.2 0.5 2 8 glycerol 0,4 Acetylacetone 0.4 N 0.88 3 8 ethanolamine 0,8 Zn (acac) ₂ θ »2 7.11 4 8 ethanol 0,5 water 0,3 Al (acac) j 0.2 9.32 5 8 ethanol 0,4 Acetylacetone 0.4 Zr (acac > 2 0.2) 8.81 6 8 Acetylacetone 0.8 More than 0.2 10.25 7 8 ethyl acetate 0.7 chromocene 0,3 6.45 8 8 Acetylacetone 0.4 Water 0.3 Mn (acac) ₂ 0.3 6.56 9 8 ethanol 0,5 water 0,3 Co (acac) ₂ 0.2 0.38 10 8 cyclohexanol 0.4 acetylacetone 0.4 n 0.99 11 8 ethanol 0,75 Fe (acac> 2 0.25 7.74 12 • 8 ethanol 0,2 Acetylacetone 0.6 Cobalt (II) 2-ethylhexanoate 0.2 2.35 13 8 « cobalt ethylacetoacetate 0,2 0.70 14 8 M ferrocene 0,2 5.7 15 Dec 8 water L, 8 Ni (acac) ₂ 0.2 4.18

Claims (3)

OBJECT OF THE INVENTION! 225 437 CLAIMS 1. Amine hardeners for solutions of epoxy resins in unsaturated monomers, consisting of a polyamine and a coordination metal compound, capable of crosslinking epoxy resins and polymerizing an unsaturated monomer in the presence of an organic peroxide, characterized in that they consist of 80 to 99.7% by weight. % polyamine having a relative molecular weight of 60 to 1000, containing at least three amine hydrogens per molecule, 0.2 to 20 wt. % water and / or an alcohol or an ester thereof with a monocarboxylic acid and 0.01 to 10 wt. coordination compounds of metals I. to VIII. groups of the periodic system · 2. Amino hardeners according to claim 1, characterized in that they contain as a coordination compound cobalt, copper or iron acetylacetonate. 3. Amino hardener according to claim 1, characterized in that it contains water and / or ethainol in addition to cobalt, copper or iron acetylacetonate.