DE1595815C3 - Process for the production of moldings based on triglycidyl isocyanurate - Google Patents

Description

a) 60 to 90 parts by weight of triglycidyl isocyanurate with an epoxy oxygen content of at least 14%, optionally by reaction with mono- or dibasic carboxylic acids or epoxidized carboxylic acids has been modified, and / or with a crystallized triglycidyl isocyanurate, the optionally modified by reaction with monohydric phenols and / or thiophenols modified glycidyl isocyanurate having an epoxy oxygen content from 8 to 14%,

b) 40 to 10 parts by weight of a liquid, low molecular weight mono- to divalent glycidyl compound,

c) 20 to 30 parts by weight of a liquid organic amino compound,

d) where appropriate, other auxiliaries

and the mixture obtained is allowed to react at room temperature.

It is known to produce curable mixtures from crystallized triglycidyl isocyanurate and substances known for polyadduct formation with epoxy compounds. In most cases, these mixtures have to be cured at higher temperatures, for example between 150 and 250 ^° C., for a relatively long time. It is also known to produce mixtures based on triglycidyl isocyanurate with carboxylic acid anhydrides which cure even at lower temperatures. However, when curing these mixtures, it is necessary to use addition compounds of ßortrifluorid and caprolactam in addition to carboxylic acid anhydrides.

The invention is based on the object of providing low-melting or liquid to pasty Mixtures that cure at room temperature for the production of moldings based on triglycidyl isocyanurate to find where the valuable properties of triglycidyl isocyanurate resins largely are preserved.

The invention therefore relates to a process for the production of moldings based on triglycidyl isocyanurate and substances known for adduct formation with polyvalent epoxy compounds, optionally in the presence of accelerators, dyes or fillers, which is characterized is that one mixes with one another

a) 60 to 90 parts by weight of triglycidyl isocyanurate with an epoxy oxygen content of at least 14%, which is optionally obtained by reacting rr, mono- or dibasic carboxylic acids or epox Dated carboxylic acids has been modified, uni- or with a crystallized triglycidy isocyanurate, which is optionally obtained by reaction with monohydric phenols and / or thiophenols modified, modified glycidyl isocyanurate obtained with an epoxy oxygen: content from 8 to 14%,

ίο b) 40 to 10 parts by weight of a liquid down molecular mono- to divalent glycidyl compound,

c) 20 to 30 parts by weight of a liquid organic Amino compound,

d) where appropriate, other auxiliaries

and the mixture obtained is allowed to react at room temperature.

For the M to be used according to the invention; Crystallized triglycidyl isocyanurate ^ with an epoxy oxygen content of at least 14%. The production of such pro ducts is known per se and can be removed from crude reaction products by cleaning agents such. B. by

Reaction of cyanuric acid with an excess of epichlorohydrin obtained. If necessary, it can be recrystallized once or several times from suitable solvents such as methanol, a product with the required epoxy content can be produced.

Modified glycidyl isocyanurates can also be used for the process according to the invention. By modifying the triglycidyl isocyanurate, products with a lower melting point and usually better compatibility with the other components are obtained. The glycidyl isocyanurate to be used according to the invention can be reacted with monohydric or dihydric phenols and / or thiophenols. For every 10 moles of triglycidyl isocyanurate, 1.5 to 6 moles of pheno ^! or thiophenol are consumed. Another method of modifying the triglycidyl isocyanurate is to react it with mono- or polybasic carboxylic acids or epoxidized carboxylic acids. There should be 1 to 10 carboxyl groups for every 30 epoxide groups of the triglycidyl isocyanurate.

The low molecular weight monovalent to divalent glycidyl compounds used according to the invention can be used for Mixtures of the glycide compounds known as so-called reactive diluents are used such as stearyl glycidyl ether, stearic acid glycidyl ester, Hexanediol diglycidyl ether, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, terephthalic acid diglycidyl ester. Conventional low molecular weight liquid epoxy resins based on diphenylolpropane can also be used in smaller quantities. Liquid glycidic compounds are preferred, e.g. B. Phenylglycidäther, Butylglycidäther, Octylglycidäther, Glycidyl benzoate, styrene oxide and octene oxide. Furthermore, there are also low molecular weight ones divalent glycidic compounds in question, such as butanediol diglycid ether, adipic acid diglycidyl ester, Diglycidyl sebacate, diglycidyl phthalate, Ν, Ν-diglycidylaniline.

The most varied of compounds are suitable as organic amino compounds, one or the other several primary and / or secondary and / or ter-

3 4

contain tiary amino groups. The amino compounds can be used as casting resins, molding compounds, adhesives, and can be both aliphatic and cyclic putties, coating materials and as a coating structure. The cyclic amines can process both materials. Furthermore, the cycloaliphatic, aromatic and heterocyclic mixtures with or without a solvent can contain rings after impregnation. Furthermore, such amines can be used to process fibrous webs into laminates, which have various of the aforementioned They show excellent adhesion to metal, such as rings. The amino nitrogen in heterocyclic aluminum, iron, copper, nickel, chromium, zinc, see amines, can also be a component of the ring made of brass, titanium, and also on glass, stones, and concrete. Examples of the mentioned primary and secondary ceramics, wood, plastics such as polyvinyl chloride, dear amines are the following: propylamine, hexylamine, io hardened melamine resin, urea resin, phenolic resin dodecylamine, benzylamine, ethylenediamine, propylene and hardened polyester resins,
diamine, butylenediamine, diethylenetriamine, triethylene moldings, which are made from the according to the invention to be

Tetramine, dimethylaminopropylamine, diethylamino-reversing mixtures produced, propylamine, 1,2- or 1,4-diaminocyclohexane, 1,2-di- show good thermal and mechanical properties. amino-4-ethylcyclohexane, l-cyclohexyl-S ^ -diamino- 15 Are bonds with the according to the invention to cyclohexane, 4,4'-diaminodicyclohexylmethane. Using mixtures carried out, it is also useful to use condensates of aniline with form-appropriate, the materials to be bonded under aldehyde. Also suitable are polyamides holding free amino groups at a low pressure of 0.05 to a few kp / cm ^a , in particular combining the reaction. Even after a relatively short time, products made from dimerized fatty acids and poly-20 achieve good strengths,
amines, which in addition to free amino groups also In the following examples, the Martens

May contain imidazolidine rings. temperature, impact strength, deflection,

It is also possible to use those amines for the flexural strength and the tracking resistance according to the appropriate implementation which contain further DIN 53 458, DIN 53 453, DIN 53 452 and DIN 53 480 functional groups, such as, for example, 25 have been measured.
Ethanolamine, propanolamine or the reaction products of amines with ethylene oxide, propylene oxide,

such as N- (hydroxyethyl) -l, 2-diaminopropane, Example 1

N- (hydroxypropyl) -m-phenylenediamine, N, N'-di- (hy-

droxybutyl) diethylenetriamine. Furthermore are suitable 30 It was a liquid, good at room temperature 4,4'-Diaminodiphenylsulfid, Dicyanäthyläthylendi- pourable mixture made from 70 g of triglycidylamine, 1,4-bis (y-aminopropoxy methyl) -cyclohexane, isocyanurate (technical mixture of high and low-N- (4-hydroxybenzyl) -ethylenediamine, N- (4-hydroxy- melting form; epoxy oxygen content 15.5%), benzyl) -diethylenetriamine. 17 g of butanediol diglycid ether, 13 g of a liquid

The amount of amine hardener to be used, epoxy resin based on bisphenol A (epoxy can vary widely within wide limits. It is equivalent to 190), 48 g of 4,4'-diaminodicyclohexylmethane. However, it has been found to be expedient to generally use such amounts of the mixture described above that on a test specimen that was cast after 24 hours there was approximately a reactive epoxy group that was capable of being demolded. After heating at 150 ⁰ C lOstündigem an amino nitrogen bonded hydrogen atom were measured 40 the following values:
not applicable.

Especially when using a less reactive Martenen temperature 191 ° C

tive organic amino compounds it can ..., :

Shortening the reaction time occasionally expedient - impact strength 6 kp cm / cm ²

be moderate to heat the mixes a little, with a deflection of 3 mm

for example at temperatures from 50 to 110 ° C. Flexural strength 555 kp / cm ^a

can affect the final properties of the hardened mixtures
can be reached faster. In addition, so-called accelerators can also be used, e.g. B. Hydroxyl Example 2
group-containing compounds such as phenols, 50

tertiary amines or phosphines, such as N-alkyl- For this example, modified glycidyl iso-

piperidine, 2,4,6-tris- (dimethylaminomethyl) -phenol cyanurate used, which is produced by reaction of 150 g or triphenylphosphine. As further been accelerator triglycidyl isocyanurate with 22.2 g of propionic acid wähkommen quaternary ammonium bases or their rend 3 hours at 120 to 13O ⁰ C obtained salts such. B. Benzyltrimethylammonium hydroxide was 55 (EV value 151). Various amounts of butane-phosphonium salts were possible for this modified glycidyl or salts of this base or sulfonium salts or isocyanurate. dioldiglycidether and 4,4'-diaminodicyclohexylme-

Than given to the mixtures to be used according to the invention. The well-castable mixtures are erkönnen dyes or fillers added cured for 24 hours at room temperature, such as alumina, silica 60 were acid after a post-treatment at 9O ⁰ C, clay, stone dust, ground dolomite, ~ 'for 24 hours, the values measured from the following asbestos, titanium dioxide, magnesium oxide, soot, iron oxide table,
and others more. In the table, the first column shows the amount of

set of metal powders, such as modified glycidyl isocyanurates (mod. GI), des Iron powder, zinc powder, aluminum powder, titanium 65 butanediol diglycidether (BGÄ), diaminodicyclo powder. hexylmethane (DDM). Then come the

The mixtures to be used according to the invention Marten temperature, the impact strength, the throughput are cured while shaping, d. i.e., flexure and flexural strength.

mod. GI BGÄ DDM Martens impact deflection bending

temperature toughness bending strength

(° C) (kp cm / cm ¹ ) (mm) (kp / cm ² )

90 G B. 10 g 35 G 142 13th 84 G 16 g 36 G 129 14th 76 G 24 g 37 G 117 17th example 3 72 g 4 ,.

For this example, isocyanurate modified with phenol was used, which had been obtained by reacting 200 g of triglycidyl isocyanurate with 12.6 g of phenol at 140 ° C. for 2/2 hours. The reaction product was after cooling to room temperature with 53 g of butanediol-1,4-diglycidyl ether and 5
7th
8th

910 1120 1130

4,4'-Diaminodicyclohexylmethan added. The mixture became test specimens at room temperature poured and kept at this temperature for 15 hours. Then it was demolded and another 32 hours annealed at 100 ° C.

An average Marten temperature of 60 ° C. and an impact strength of 8 kp · cm / cm ^{2 were} measured on various test specimens.

Claims (1)

Claim: Process for the production of moldings based on triglycidyl isocyanurate and for Adduct formation with polyvalent epoxy compounds known substances, optionally in Presence of accelerators, dyes or fillers, characterized in that that one mixes with one another