DE2335550A1 - Single liq epoxy resin compsn - curable by water contg cyclic Schiffs base used as adhesives, paints, for boat repairs etc - Google Patents

Abstract

Title compsn. comprises a condensation prod. of a polyol and/or bisphenol A with epichlorhydrin, and an aliphatic Schiff's base of general formula (I): (n is 3-11), the proportion of the Schiff's base being 15-40 mol.% (based on no. of epoxy gps. in the epoxy resin). The ring in the Schiff's base opens in the presence of water, forming highly reactive amine gp., which crosslinks the resin.

Description

The present invention relates to a liquid one-component Epoxy resin preparation that can be easily hardened by reacting with water.

It was previously known that polyoxyran compounds .., which contain two or more oyran groups and which have been obtained by reacting polyphenols with epihalohydrins (these Compounds are called "epoxy resins" below) with a curing agent which reacts reactively with oxyrane groups is, like polycarboxylic acids, whose anhydrides, polyamine compounds or polyamidoamides react and a cured epoxy resin deliver which has excellent physical properties. Such epoxy resins have a wide variety of uses in found in numerous areas of application as paints, molding compounds, adhesives, in civil engineering and construction technology.

However, epoxy resins are known to be very difficult to cure underwater or on wet surfaces, so that they could not be used in construction and other outdoor work in the rainy season in the past because they were underwater or in the presence of water do not have sufficient adhesion. Recently, however, numerous types of epoxy resin preparations which can cure even under water or under humid conditions have become known, de are modified as curing agents with amines and contain water-repellent additives or the like. These epoxy resins of the known type, which are curable under water, are two-component systems and have numerous disadvantages such as poor curing, short pot life and the like. So far, no satisfactory epoxy resin preparations have been obtained.

With the above various problems in mind, numerous studies have been made in order to obtain a Epoxy resin preparation of a liquid one-component system, which can be hardened in the presence of water and is excellent Properties has to be found. As a result, the "above mentioned disadvantages can be eliminated by the present invention.

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It is an object of the present invention to provide a liquid one-component epoxy resin preparation To provide that excellent adhesion even under water or on having damp surfaces. Other objects and advantages of the present invention will become apparent from the detailed description that follows emerge.

The above-mentioned goals can be achieved by an epoxy resin preparation. which contains the following two components. The first component is selected from a group of condensates of 2, 2 '-bis (4-hydroxy-phenyl) propane and epichlorohydrin, glycidyl ethers of polyols and mixtures thereof.

The second compound is an aliphatic see base with the ship general formula:

(CHJ _n - C - (CHJ - NH ₉

IN

where η has a value of 3-11, in an amount of 15-40 mol%, based on the oxyran oxygen contained in the first component. *

It is actually surprising that the above discussed. Preparation of the present invention as a liquid one-component preparation can be used, which is curable both under water and on damp surfaces and which in addition still has excellent adhesion properties. These surprising advantages of the present preparations can on the one hand to the unique functions of the aliphatic Schiff base with the general formula given above which opens its ring as soon as it comes into contact with water and thereby supplies a highly reactive amino group and thereby causes a crosslinking with the epoxy resin.

Another important point of view to be taken into account is the fact that the free amino group initially present reacts immediately with the epoxy compound and thus represents an amine as a hardening agent, which is insoluble in water and moreover has not yet caused gelation.

Suitable epoxy resins can be used those having one or more adjacent Oxyrangruppen, preferably glycidyl ethers of a polyphenol, in particular 2, 2 as a first component in the above-described preparation of the present invention, '- bis (4-hydroxyphenyl) propane and the glycidyl ether of a polyol , especially diglycidyl ethers of ethylene glycol and glycerine.

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As an aliphatic vessel, see bases as the second component of the epoxy resin composition of the present invention and which act as curing agents are suitable those which Have 5-13 carbon atoms in a ring. So, different curable preparations can have different specific Have formations obtained by varying the number of carbon atoms in the ring. So by using a Schiff see base, which has a lower carbon content in the ring, a preparation can be obtained that is relatively quick a hard product cures when such a product is needed.

On the other hand, when a cured product having sufficient elasticity is required, a higher one is to be used Homologues useful even if it takes a relatively long time to cure. It is therefore only necessary to have such connections to choose the appropriate one depending on the specific purpose for which the curable mixture is to be used Have numbers of ring carbons.

Such Schiff bases can easily be produced by any known method, for example by implementation of lactams and / or their polymers with an alkali metal, an alkali-earth metal oxide or hydroxide or their mixtures. For example, they can be made by reacting lactams and / or their polymers with a carbon ring containing 5-13 carbon atoms has, or, in the case that a branched chain is present, has 6 or more carbon atoms for a branched chain, such as lauryl lactam, caprolactam, enanthlactam, 5-methyl-> £ caprolactam, g- caprolactam and pyrrolidone lactam with calcium hydroxide, Calcium oxide, barium oxide, magnesium oxide, sodium hydroxide or the like can be produced.

Differences in the method of making the Schiff base are for use in accordance with the present invention without Concern.

Each Schiff base which is used according to the present invention as the second component is calculated in moles in an amount of 15-40 mol%, preferably 20-30 mol%, based on the oxirane oxygen content contained in the first component is used. If the preparation is hardened under water or on a damp surface, gelation takes place during the phase of a low degree of polymerization and the main hardening reaction continues in the gel. This places a restriction on the diffusion of the ship's base. It is therefore proposed to favor the reaction to use the Schiff base in excess of its chemical equivalent . However, if the ship see base in a surplus! If more than 40 mol% is used, it has negative effects

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in relation to the physical properties of the curable preparation. A Schiff ³ see base opens its ring easily when it is in contact with water and converts to a diamino alkanone. Under non-aqueous conditions, however, only the first free primary amine group can react with the oxirane group, so that no further progress occurs in the curing reaction, which could result in gelling of the system. For this reason, the preparation can be stored in an extremely stable state for a "long period of time. However, when this preparation is used under water, the free active amino group generated from the Schiff base in contact with water through ring opening reacts with the oxirane group of the epoxy resin immediately to bring about crosslinking and thus curing.

In construction work carried out under water or during the rainy season, where the formulations of the present invention are particularly effective, it is occasionally necessary to carry out the curing process under very adverse conditions, such as. z. B. at a very low temperature, with the additional requirement that the curing has to take place in water or under humid conditions. Even under such unfavorable conditions, the preparation of the present invention can fully achieve its effectiveness provided that the temperature is 15 ^° C. or higher. But by adding a third component in an amount of 2-15 parts by weight to 100 parts of the first component, which is an aliphatic or aromatic tert. Amine compound having an N atom, such as. B. trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine and dimethylaniline or a quaternary ammonium compound such as tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide can favor the curing reaction so that it can be carried out even at lower temperatures.

Likewise, in the preparation of the present invention, the Use of halides or organic compounds of titanium, aluminum, tin, zircon, zinc, cadmium, manganese, iron, Chromium, vanadium, antimony, bismuth, boron, silicon or the like. ' instead of the tertiary or quaternary amines mentioned above or particularly recommended as an additive to these amines. These compounds include, for example: titanium tetrachloride, Tetrabutyltitanium, titanium tetrabutoxide, diethyldichlorotitanium, aluminum chloride, Triethylaluminum, aluminum triisopropoxylate, tin-2-chloride, Tin-4-chloride, dibutyi-tin, tin-diethoxide, tin-2-oxalate, Zinc chloride, diethyl zinc, antimony pentachloride,

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Antimony trichloride, triethyldibromoantimony, ferric chloride, Chromyl chloride, tributyl bismuth, boron fluoride, monobutyl difluoroboron, trimethyl-N-methylaminosilane and hexaphenylcyclotrisilazane.

It should also be noted that when using the preparation of the present invention, no special or any additional precautions must be taken _three known not heard of the use of such conventional additives such as diluents, curing accelerators and additives in itself.

The preparation of the present invention obtained in the manner obtained above is a liquid one One-component system and can be used on surfaces not only in the presence of normal water, but also in the presence of Find sea water use. Possible uses exist, for example, as an adhesive, paint coating agent, reinforcing agent, Repair material, molding compound and especially as reinforcement and repair material for steel, for steel structures and for ship floors, which can be used in normal water as well as in sea water, whereby the relatively fast curing is sufficient and peaceful in the water.

The present invention is illustrated in detail by the following examples described.

Examples 1 to 6

In the following table 1 the physical properties of resin preparations are shown by mixing certain amounts of a condensate which contains 9.2% oxirane oxygen and has been made from bisphenol A and from epichlorhydin and with Schiff bases, such as indicated in the table below, have been produced and have been cured. After three days, the cured mixture was kept for a further seven days in water at 20 ⁰ C, the physical properties of the resin material obtained are again given in Table 1.

409885/1175

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Note: Methods for determining the physical Characteristics:

1) Shows the amount (parts by weight) of the second component per 100 parts by weight of the first component

2) Measured with a Barcol no. 936

3) Measurements were made using test pieces of 18 mm × 18 mm × 900 mm

4) The measurements were made using test pieces of 15 mm 15 mm 900 mm with a Charpy impact tester.

As can be seen from Table 1, the cured specimens have different physical properties depending on the number of carbon atoms that. in the ring of the ship ³ see base are included. More specifically, the specimens have a greater hardness when they were obtained from such a Schiff base containing a small number of ring carbon atoms, while test specimens having a greater impact strength from Schiff ^{3 received} bases with a larger number of ring carbon atoms will. In addition, an extremely small amount of Schiff base prevents the preparation from hardening, while an excess amount only provides brittle test specimens. It should therefore be noted that the amount of Schiff ³ see base which is mixed is preferably in the range of 15-40 mol%, as has already been explained in the present invention.

Examples 7-11

A preparation was made from 26 parts by weight

₅ -C- (CH ₂ I-NH ₂

ur

and 5 parts of various tertiary amines or quaternary amino compounds and 100 wt. parts by a mixture consisting of 91 wt.% epoxy resin having an oxirane oxygen content of 9, 2 ⁰ Io which has been prepared by condensation of bisphenol A and epichlorohydrin, and consists of 9% by weight diglycidyl ether of glycerol. After adjusting the temperature of the samples of the above preparations at 10 ⁰ C and 25 C were by brushing, each applied in an amount of 2 kg / m ^ _j iron plates, immersed in water and held. The results obtained are shown in Table 2 below.

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Table 2 Hardening Added Condition for the coating
at 10 ° C and 25 ° C Fully in water Complete 2335550
II accelerator lot
(Parts) at 10 C constant
Curing at 25 C .Curing - - grabbed 87 h grabbed 46 hours example Triethylamine 5.0 16 hours 60 6 hours 32 9885/1 1 7th Tri-n-butylamine 5.0 10 56 4th 30th cn 8th Dimethylaniline 5.0 . .8th 52 .4. ... 27 9 Trimethylbenzyl
Ammonium hydroxide 5.0 7th '' 45 '' ■ '. . 3. 22nd 10 5 2 11

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From Table 2 it can be seen that the addition of a tertiary amine or a quaternary amino compound to the preparation of the present invention to shorten the curing time in Water contributes especially at lower temperatures.

Example 3

An iron plate immersed in water at 10 C 'was placed in the In the same way as described in Example 2, coated, but with the difference that 3 parts by weight of the preparation curing accelerators mentioned below instead of the corresponding tertiary or quaternary amino compounds, which are used in Example 2 were used.

Table 3 Hardening accelerator

Titanium tetrabutoxide, triethylaluminum, dibutyltin, diethylzinc, boron trifluoride Antimony pentachloride iron III chlorine id titanium tetrachloride / tri-n-butylamine (1: 2 weight ratio) Triethylaluminum / ethylamine (1: 1 in weight ratio).

All of the above formulations were contact-proof within 2 hours and they fully cured within 36 hours. the end. From this it can be seen that by using these curing accelerators shown in Table 3, the Complete hardening of the preparation takes more time than when using the tertiary or quaternary amino compounds is the case, but that the preparation containing these hardening accelerators quickly solidifies to contact. Hence these are Preparations suitable, for example, for repairing water leaks in ships.

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Claims (2)

- 10 - File 2318 Patent Claims Curable epoxy resin preparation characterized by the content of the following two components: 1) The first component is selected from a group consisting of a condensate of 2, 2 -bis (4-hydroxyphenyl) propane and epi chlorohydrin, a glycidyl ether of a polyol or mixtures thereof. 2) The second component is selected from the aliphatic Schiff bases of the general formula (CHJ - C - (CH) - NH Δ η λ Δ η Δ where η has a value of 3-11, in an amount of 15-40 mol%, based on the oxirane oxygen contained in the first compound. 0 9 8 8 5/11 7 ',