DE2439469A1 - USE OF HARDENABLE MIXTURES - Google Patents

Description

Priority: August 17, 1973, France, no.73.30659

Use of curable mixtures

The invention relates to curable compositions which are predominantly composed of Coal pitch and curable resins exist, as well as the use of these materials for the production of solid masses or bodies that can be easily smashed and removed, in particular from filling compounds for Verbiädungsteile of electrical power transmission systems. The materials according to the invention represent an improvement and an advantageous embodiment of the filling compounds described in the German patent application> P 2256615.0 are described.

According to the main patent (German patent application P 2256615.0), cold-pourable masses which can be hardened without the application of external heat were made available, which can be used to achieve removable bodies. These materials essentially contain a crosslinkable resin, a reactive diluent, a hardener for the resin and, what is essential, at least 50 percent by weight of coal pitch, the preferred proportion of which is between 50 and 70 % . For the production of these known materials, the formation of a two-component system has been proposed, one component containing the resin, the diluent and the coal pitch and the other component the hardener, and the two components being mixed at the moment of their use. The first component is obtained by first melting the pitch by heating and then adding the resin and the diluent to it.

On the other hand, it is known to use mineral or organic materials in the production of fillers obtained from curable resins Mix in fillers, such as glass beads, gravel are suitable

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neter particle size, grains of rubber or various Polymers and the like. In this way, the volume of the resin to be used is also reduced, thereby reducing manufacturing costs to be humiliated. However, the presence of these fillers results in a heterogeneous structure of the final result Materials whose mechanical and electrical properties are then modified.

The invention is based on the object of addressing these disadvantages avoid, especially in the case of the materials described in the main patent (patent application P 22 56 615.0). This object is achieved according to one embodiment of the invention in that pitch in the form of a solid as a filler is introduced into these materials. Using this method, the pitch content of the resulting masses can be increased. These materials nevertheless retain their homogeneous structure because under the action of the heat released by the crosslinking reaction of the curable resin, the solid pitch passes into a fluid state and is distributed homogeneously in the mixture. The mechanical and electrical properties of the cured materials are not appreciably modified in this way.

However, its use as a filler material is not the only way of applying solid pitch to the field the materials described in German patent application P 2256615.Ό to be discribed. According to another embodiment of the invention, the pitch is also in solid form in the manufacture of this Materials used instead of melting it beforehand, as is done in the known method. The manufacture of the Materials is therefore simplified and made more convenient. It goes without saying that both methods can also be combined and the materials can be made using coal pitch, some of which is in molten form and is partly in solid form.

According to an essential feature of the invention, the pitch is therefore from the start in solid form in the mixtures that ne ^

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Ben this component contain a crosslinkable resin, thinner and a hardener.

In this description, under "pitch in solid form" the Product of solid consistency, as it is at room temperature, in the form of blocks, grains of various dimensions, or powder. As discussed above, the use of pitch in this form enables one Increasing the content of this component in the materials. With the help of this measure, a total content of 75 percent by weight can easily be achieved or more can be achieved. You can of course stay within the limits of the German one Patent application P 2256615.0 are given, in particular, if the solid pitch is used only for the purpose of making it easier Achieve manufacturing method for the materials. However, the minimum proportion of 50 percent by weight should be adhered to because it is the critical factor by which the cured masses have low impact strength and suitable have electrical properties that make them suitable for use as fillers to make suitable in electrical power transmission networks.

The other components of the materials, namely the liquid crosslinkable resin, the diluent and the hardener, can be the same as those described in German patent application P 22 56615.0. Thus, the resin is advantageously selected from aliphatic, cycloaliphatic chosen ^ or aromatic bi- or trifunctional epoxides, with a preferred compound of Diglycidylather of 4.4 ^f is -Diphenylolpropan. The reactive diluent used is a monoepoxy compound, such as an alkyl or aryl glycidyl ether, in particular butyl glycidyl ether, phenyl glycidyl ether or styrene oxide. Cresyl glycidyl ether can also be an excellent diluent. AJL's hardeners are preferably used in connection with epoxy resins containing amino groups with mobile hydrogen, such as diethylenetriamine, triethylenetetramine, metaphenylenediamine and the like, or also sulfurized derivatives. Finally, »various additives such as hardening agents can also be added to these various constituents.

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■ accelerators, surfactants, adhesion improvers, as explained in German patent application P 22 56615.0.

The practical implementation of the use according to the invention of pitch in solid form can be obtained by various methods. According to a first method, this component becomes dispersed in the liquid ingredients. In this case, the pitch is the mixture of crosslinkable resin and diluent incorporated and then, at the moment of application of the materials, the hardener is added and the potting takes place made of the application. You can just as easily add the pitch to the mixture of crosslinkable resin, thinner and hardener insert immediately before potting. According to another possibility, the solid pitch is first placed at the application site and then pour the liquid components together. According to one Another embodiment, according to which the pitch is used combined in the molten state and in the solid form in accordance with the information in German patent application P 22 56615.0, a two-component system is produced and added then add the solid pitch, which can be done by putting it in one of the ingredients or in the two previously mixed ingredients suspended, or by presenting it at the application site. If you use this third method, you can Use resin-based constituents, which from the outset contain proportions of pitch that match those in the German Patent application correspond to specified amounts. The pitch added in solid form is simply an additional amount, which increases the total pitch content in the materials, according to one of the aims of the invention and according to one preferred embodiment. However, the resin-based ingredients may contain a smaller proportion of this product, which is even below 50 percent by weight of the total liquid Components can be., Since the pitch present in solid form supplements this amount up to the desired proportion, the but in each case at least 50% by weight of the final Must be mass. Any additives used are finally added, as in the German patent application P 22 56615.0 is described.

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The grain size of the solid pitch used according to the invention varies depending on the particular. Intended use. . * In general, however, it is preferred to use a finely divided product, for example a powder with a small grain size, when adding the pitch to the liquid components and / or when using a relatively large proportion. If vice versa the amount is lower and / or if the product is presented at the place of use, materials with higher Grain size are used. One pitch is used, its The softening point is close to the temperature reached when the resin is crosslinked by the hardener.

The following examples illustrate the various embodiments of the invention described. In these examples the percentages given are percentages by weight.

example 1

A two-component system is produced which contains the following components:

Component a): 60 % coal pitch with a softening point

The 20% 4.4 was KS (Kramer Sarnov) of 38/41 "previously melted by heating to 100 ° C, ^r -Diphenylolpropan-diglycidylather and 20% CresyIglycidylather;

Component b): 55 % triethylenetetramine, 27.5 % phenol and 17.5%

Pine oil

If these two components are combined in the weight ratio a / b = 10/1, the pitch content of the final mixture is 55 fi. A mixture of 4700 g (a) and 470 g (b) takes up a volume of 4.3 liters.

According to the invention, 1300 g of pitch crushed into blocks and having a softening point are used in the mixture described above KS 70 dispersed. This material occupies a volume of 5.2 liters. His total pitch is $ 63.5 '. It hardens within 1 hour 15 minutes, the crosslinking temperature of the resin reaching 110 ° C. The hardened mass obtained is slightly

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acceptable and very homogeneous.

The same results are obtained if the crushed first Pitch is added to the container to be filled with the filling compound and then the mixture of the two components is poured.

Example 2

Hard coal pitch with a softening point KS 100, which is in the form of grains, the largest dimension of which is less than 2 mm, is dispersed in a mixture of 4,4 • -diphenylolpropane diglycidyl ether and styrene oxide. The respective proportions of these ingredients are 75, 22 or 3% · the other hand, to a second component forth that contains $ 55 of triethylenetetramine, 27.5 f> phenol and 17.5 f pine oil.

The two components are used in a weight ratio of 10 parts by weight of the first component to 0.8 parts by weight the second component mixed together. The resulting mixture contains $ 69.4 of pitch. The mixture is poured into a mold, which is easy to do. The hardened mass finally obtained can be easily removed.

The materials accessible according to the invention can be used for all purposes that are described in the German patent application P 22 56615.0 are provided, that is, in all cases when a material with the help of a cold casting process a hardened mass is to be isolated or protected, which can easily be smashed again. A particularly important type of use is the application of these materials for the production of filling compounds for components of line networks for electrical Energy, for example for junction boxes for cables.

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Claims (4)

Claims l) _J / Use of mixtures which can be hardened without external heat input and which contain at least one crosslinkable resin, a reactive diluent, a hardener and at least 50 percent by weight of coal pitch, according to the main patent (patent application P 22 56 615.0), for the production of hard, easily removable bodies, characterized in that mixtures are used in which the coal pitch is wholly or partly in solid form. 2) Use of mixtures according to claim 1 for the preparation of Filling and insulating parts for connecting pieces in electrical line networks. 3) Use according to claim 1 or 2, characterized in that that one adds the coal pitch in solid form to the liquid components when using. 4) Use according to claim 1 or 2, characterized in that the coal pitch is used in the application Submit the mixture in solid form at the place of application and pour in the liquid components. 509812/0749