LU82641A1 - POLYMER COMPOSITIONS RESISTANT TO ELECTRIC EAGGLES AND WATER EAGLES - Google Patents

Description

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The present invention relates to polymeric compositions having increased resistance to electric egrets and water egrets and which are useful as insulators for electric cables.

; Polymeric compositions are well known and are widely used as insulators for wires and cables. As an insulator, it is important that the composition has various physical and electrical properties, for example resistance to mechanical sinking, resistance to stress cracking and dielectric breakdown. Recent publications indicate that the development of water egrets and electric egrets in the insulation is a particularly significant drawback, as it is associated with dielectric breakdown, although it is not necessarily entirely responsible for it .

An important application of an insulating material relates to high voltage transport and distribution cables, especially in the ground, and three types of egrets have been observed in electric cables: electric egrets, electric egrets. water and electrochemical egrets.

25 It is generally believed that electric egrets are caused by corona discharges causing melting and breakdown of the polymer, while water egrets are usually seen in cables buried in damp places and have a different appearance. electric egrets. Electrochemical egrets are similar to water egrets, but are characterized by the presence of metal ions.

US Pat. No. 4,144,202 aims to inhibit the breakdown of water with dielectric materials / ï, t · * 2 ï * based on ethylene polymers. This patent describes electrical faults caused by egrets and explains the nature of egrets and some of their causes. In general, as the poly-5 mother composition slams, the damage progresses through the insulator or the dielectric following a more or less arborescent course. The egret is usually a slow deterioration and can take years to cause insulation failure. As indicated in the above-mentioned patent, the water egret is inhibited in ethylene polymer compositions by including certain organosilanes. In particular, the organosilane is a silane containing an epoxide radical. The cited patent describes suitable polymers, adjuvants and processing methods for the preparation of the composition.

In US patent applications Nos. 709266 and 809 910, it is a question of an insulator particularly suitable for high voltage electric cables 20 and containing an effective amount of an alcohol containing 6 to 24 carbon atoms, which gives the composition resistance to the development of electric egrets.

These applications, as well as the aforementioned US Pat. No. 4,144,202, describe the problem of electric egrets in polymer compositions and cite numerous patents which attempt to solve it. There are mentioned suitable polymers, adjuvants and methods of preparation.

DE-OS 2 737 430 teaches that certain * 30 alkoxysilanes, added to a polyolefin insulator, prevent the egrets. It says that several trimethoxysilanes and triethoxysilanes are useful. It is not stated or suggested that alkoxyalkoxy silanes have the property of inhibiting both water and electric egrets. ^ y) * 3

US Patent 3,553,348 and GB Patents 1,248,256 and 1,277,378 relate to inorganic filler polymer compositions useful as insulators for electrical wires and cables. The mineral filler is treated with an organosilane such as an alkyl alkoxysilane or vinyl alkoxysilane to decrease the porosity of the composition. None of these patents indicate or suggest that the addition of an organosilane to a The uncharged polymer composition advantageously increases the resistance of the composition to the formation of water and electric egrets.

Unfortunately, however, the prior art does not provide an insulating composition having both increased resistance to water egrets and electric egrets. As indicated in US Pat. No. 4,144,202 already cited, intrinsic electrical breakdown, damage by crown effect, by electric egret and by water egret are different, the mechanism is different each time and a different solution is required. to obtain an improvement in a dielectric material for each deterioration mode considered. A considerable problem for technicians is therefore to find a single composition * which is capable of withstanding both electric and water egrets.

Unexpectedly, it has now been discovered that polymeric compositions comprising an effective amount of a specific organic compound, for example a specially defined silane component, exhibit both increased resistance to water and electric egrets. . The composition can also be cured using known techniques to obtain a crosslinked composition having further improved properties for certain applications.

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In general, the polymer composition comprises, per 100 parts by weight of polymer, approximately 0.1 to 10 parts of a silane corresponding to the formula:

‘5 R - Si - R2 (a)

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R3 in which R, Rif R2 and R3 each independently represent a C1-C6 alkyl group, a C1-C6 alkoxyl group, a C1-C6 acyloxyl group, an optionally substituted C1-C6 aryloxyl group, an aryl group in Cg to C ^ g optionally substituted, a hydrogen or halogen atom, an epoxide radical, a C2 to CQ alkenyl group, a nitrogen radical, a carboxyl radical, a radical with a mercaptan X5 group or an etherified radical, provided that at least one and preferably at least three of the symbols R, R ^, R2 and Rg, for example all four, represent a group containing at least one electron donor atom in a position not adjacent to the atom of 20 silicon. The electron donor atom can be, for example, a hydrogen, nitrogen, sulfur atom, etc.

Oxygen is preferable because of its proven effectiveness. In a very preferential group, the donor atom <electrons is separated from the silicon atom 25 by three atoms.

A preferred composition comprises approximately 0.5 to 5 parts and, more preferably, 1 to 3 parts of silane constituent per 100 parts of polymer.

A particularly preferred uncharged polymer composition comprises a blend ///

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1 1 5 homogeneous of a polymeric component and an effective amount of an inhibitor of water egrets and electric egrets which is an organic compound corresponding to the formula i? 1 5 R2 -? - Yi <cnV Ve <B> - * '' in which R ^, and are similar or different and represent a group Y, (C H_) Y_R_, alkyl xn * n 4 o en à CQ, alkoxyl en à Cg, acylaxyle to C8, C6 to C aryloxyl. optionally substituted, aryl o xo in C to C optionally substituted, a 6-hydrogen or halogen atom, an epoxidized radical, an alkenyl group in Cg, a nitrogen radical, a carboxyl radical, a group radical mercaptan or an etherified radical, R 1 represents a C 1 to C 6 alkyl group, C 1 to C 6 alkoxyl, C 1 to C 6 acyloxyl, optionally substituted C 1 to C 6 aryloxyl, optionally substituted C 1 to C 6 aryl, an atom hydrogen or halogen, an epoxidized radical, a 20 to C8 alkenyl group, a nitrogen radical, a carboxyl radical, a radical with a mercaptan group or an etherified radical, and Y ^ are similar or different and represent 0, S or N , Z represents Si, Sn, Ti, P or B, a is O or 1 and n is 1 to 8.

This particularly preferred composition comprises approximately 0.1 to 10 parts by weight of the organic compound of formula B per 100 parts of polymer. A specially preferred composition comprises about 0.5 to 5 parts of organic compound, preferably about 1 to 3 parts, per 100 parts of polymer. The subject of the invention is also a method of stabilizing an electrical conductor carrying a polymeric insulator against the water egrets and the electric egrets, which consists in coating the condnc / y. 6 amount of an effective amount of a polymer insulating composition constituting a homogeneous mixture of a polymer component and an egret inhibitor which is a compound corresponding to formula B defined above.

The compositions of the invention are particularly useful in high voltage transport and distribution cables, but they are useful in other electrical applications where a remarkable combination of resistance to egrets is required. water and electric egrets.

In general, polymers suitable for the practice of the invention include any normally solid synthetic organic polymeric thermoplastic resin. They include corresponding polyolefins and copolymers, vinyl polymers, olefin / vinyl copolymers, olefin / allyl copolymers, polyamides, acrylic polymers, polystyrenes, cellulosics, polyesters and fluorocarbons.

Polyolefins include normally solid polymers of olefins, particularly mono-6 <-olefins containing about 2 to 6 carbon atoms, for example polyethylene, polypropylene, poly- butene, polyisobutene, poly- (4-methylpentene) and the like. Preferred polyolefins are polyethylene and polypropylene. Polyethylene is especially preferred. A specially preferred polyethylene because of its proven efficacy is sold under the designation "NA 310" by National 30 Distillers and Chemical Company.

Copolymers of ethylene and other compounds which can be polymerized with ethylene such as butene (1), pentene (1), styrene, etc. can be used. ^

In general, ethylene represents from about 50 to less η / 3 5 of 100% by weight. / '/ f «‘ 7

Suitable vinyl polymers include polyvinyl chloride, polyvinyl acetate, vinyl chloride / vinyl acetate copolymers, polyvinyl alcohol and polyvinyl acetal.

Suitable olefin / vinyl copolymers include ethylene / vinyl acetate, ethylene / vinyl propionate, ethylene / vinyl isobutyrate, ethylene / vinyl alcohol, ethylene / methyl acrylate, ethylene / ethyl acrylate, ethylene / 10 copolymers. ethyl methacrylate, etc. In general, ethylene - constitutes at least about 25% of the weight of the mother copoly.

Olefin / allyl copolymers include ethylene / allylbenzene, ethylene / allyl ether, ethylene / acrolein, etc. copolymers.

The silane used in the polymer compositions of the invention can be represented by one or more compounds of formula h, defined above.

The organic compound used in the particularly preferred uncharged polymer compositions of the invention is represented by one or more compounds of formula B, defined above.

"A number of groups R,, P ^ and 25 useful for the purposes of the invention are given on page 43 of" Chemicals and Plastics Physical Properties-1978-80 ", published by Union Carbide Company. Examples are chlorine , methyl, ethyl, methoxyl, ethoxyl, phenyl, hydrogen, chloropropyl groups, vinyl 2-methoxyethoxyl, ^ -methacryloxypropyl, p- (3,4-epoxycyclohexyl) -ethyl, 'jf-glycidoxypropyl, acetoxyl,) f-mercaptopropyl, 'Ç'-aminopropyl, bis-hydroxyethyl - / - aminopropyl, diacrylato -' / - aminopropyl, N- (p-aminoethyl) -f-aminopropyl and 2- (Tf-trimethoxysilyl- ^ y 35 propylamino) -ethylamino-propionate. / A 'i 4 t 8

As mentioned above, at least one of the groups R, R ^, R2 and Rg of formula A contains an electron donor atom such as an oxygen, nitrogen or sulfur atom in its chain. Preferably, the electron donor atom is separated from the silicon atom by three atoms. A preferred group corresponds to the formula (OR ^ ORç.), In which represents a C1-C8 alkyl group and a C1-Cg alkyl group, a hydrogen atom, a C1-C6 alkoxyl group or a group C8 to C8 alkenyl.

A particularly preferential group is the · - group. 2-methoxyethyl of formula OCgH ^ OCHg. A preferred compound is sold under the designation "A-172" by Union Carbide Company; it is chemically defined as vinyl-tris- (2-methoxyethoxy) silane. Other groups R, ^, R2 and Rg are the ^ -methacryloxy-propyl, ^ -glycidoxypropyl, ^ -aminopropyl, bis-hydroxy-ethyl-y-aminopropyl and N- (p-aminoethyl) - ^ aminopropyl groups.

The groups R.sup.-R2 and Rg useful according to the invention in formula B, in the case where Z is a silicon atom, include examples of groups mentioned above in connection with the publication Union Carbide Company, particularly when Yi (cnH2n ^ Y2R6 is an alkoxyalkoxyl group. Among the useful silanes of formula B are ^ -methacryloxypropyl-tris- (2-methoxyethoxy) -silane, tetrakis- (2-methoxyethoxy) -silane, methyl -tris-Î2-methoxyethoxy) -silane, phenyl-tris- (2-methoxyethoxy) -silane, vinyl-tris- (2-phenoxyethoxy) -silane, vinyl-tris- (2-methylthioethoxy) -silane, and Vinyl-tris- (2-methoxyethoxy) -silane, the latter being particularly preferred. If silicon, for example, is replaced by tin, titanium, phosphorus or boron, other compounds useful in the invention are obtained. Thus, compounds can be used, such as tris- (2-ethoxyethyl) phosphite, tris (2-n-butoxyethyl) phosphite, tetrakis- (2-methoxyethoxy) -. titanium, etc, which fall within the scope of the invention.

Consequently, in the preferred organic compounds of formula B,, R 1 and R 1 each represent a group Y 4 ^ (cnH 2 n 4 Y 2 R 6 'alkyl, alkoxyl, acyloxyl, aryl or alkenyl, Rg an alkyl or aryl group, and Y2 represent O and Z represents Si or P.

Of course, when Z represents Si, a is 1 and 10 when Z represents P, a is 0.

When it is desired to use a crosslinkable polymeric composition, crosslinking may be accomplished by any of the known methods, for example by chemical means, including peroxide crosslinking, irradiation by means of accelerators. electrons, gamma rays, high energy rays like X-rays, microwaves, etc, or thermal crosslinking. The basic methods of crosslinking polymers are well known in the art and need not be described here in detail.

Conventional crosslinking agents such as organic peroxides can be used. Free radical generators * of the organic peroxide type are in particular dicumyl peroxide, 2,5-bis- '(tert-butylperoxy) -2,5-dimethylhexane, tertiary dibutyl peroxide, benzoyl peroxide, tf, o ('- bis- (tert-butylperoxy) -diisopropylbenzene, etc., as described in US Patent 3,287,312. The amount of organic peroxide, if any, ranges from 0.5 to 5.0% about the total weight of the composition, or about 0.5 to 10 parts and preferably 3 to 6 parts per 100 parts of polymer.

The slianans and organic compounds described above are useful for both thermoplastic and cured compositions / polymers, but, for / 4 *.

10 compositions intended to be cured, it is preferable that one of the groups, namely R,, R2 or R3 is an organofunctional radical, for example a vinyl group, which gives the composition better curing properties.

Small usual amounts of other additives can also be used to achieve the desired results *. Conventional antioxidants such as hindered phenols, polyquinolines, etc. can be used.

Other ingredients which may be included are plasticizers, dyes, pigments, heat stabilizers, light stabilizers, antistats, etc.

The preferred compositions of the invention are uncharged polymer compositions. The term "uncharged" means a composition which contains less than 10% of a conventional filler for polymers.

For certain applications and to meet specific specifications, the uncharged compositions may contain no charge. The compositions of the invention can therefore contain from 0 to less than 10% of filler. Consequently, fillers such as mineral fillers can be used, to this limited extent, to prepare the compositions of the invention, but, in the particularly preferred embodiment and for certain uses, the compositions do not contain no fillers.

To prepare the polymer compositions of the invention, the various ingredients can be mixed. When the organic compound and the polymeric component are mixed together to form the compositions of the invention, they are homogeneously dispersed in each other. The order of incorporation and the particular process are not critical, except that from the moment when the peroxide is added, if necessary, the temperature must be less than 130 About ° C, poiu ^ y /

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11 Avoid premature hardening of the composition. However, this precaution is classic.

Constituents can be mixed on a variety of devices including multi-roll mills, screw mixers, continuous mixers, extruder mixers and Banbury mixers.

After extruding them onto a wire or cable or other substrate, the crosslinkable compositions are vulcanized at elevated temperatures, for example above about 180 ° C., by conventional vulcanization methods.

To determine the usefulness and effectiveness of the polymeric compositions of the invention with respect to the inhibition of water and electric egrets, accelerated tests are applied.

The electric egret tests are carried out by a method similar to that which is described in "IEEE Conference Paper No. C73, 257-3 1973" by E.J.

McMahon and J.R. Perkins. In a 6.35 mm thick plate molded by compression, strips of material about 25.4 mm wide are cut. The block is machined so as to obtain a strip having parallel edges spaced 25.4 mm apart. The strip is then cut into 25.4 mm square blocks. A blunt needle and a sharp needle are inserted into opposite parallel edges at elevated temperatures so that the tips are spaced 3.2 mm apart. The insertion of the needles and the cooling of the sample are carried out slowly to avoid applying thermal or mechanical stresses to the sample.

The acute needle has a diameter at the end of approximately 5.1 μm and the blunt needle a diameter of approximately 51 λ®. Eight test tubes of each composition are prepared, which are tested simultaneously. To carry out the electric grid test, a / / 1 / "* 12 voltage of 15 kV with a frequency of 60 Hz is applied to the acute needle; the blunt needle is grounded. The time required for each of the eight test pieces to deteriorate is noted by formation of egrets and then by short-circuit. The time necessary for the deterioration of 50% of the test pieces is used to characterize the effectiveness of the tested egret retarder.

. The water egret test is carried out by a method similar to that described in US Pat. No. 4,144,202 already cited. A compression molded disc approximately 150 mm in diameter with 24 conical depressions is prepared for each composition. The geometry of the disc and the dimensions of the depressions are practically the same as in the cited patent.

On the base of the disc, a silver paint is sprayed which serves as a ground electrode. A 152 mm acrylic resin tube is clamped on the upper face, forming a test cell. About 150 ml of 0.01 N sodium chloride solution is poured into the cell and the air bubbles retained on the surface of the test piece are removed. A ring of platinum wire is then immersed in the electrolyte and it is connected to the electric source which supplies 5 kV at a frequency of * 3 Hz. The test tubes are supplied for 22 hours, then they are removed from the cell d 'test and washed with distilled water. The ten central depressions of the disc are cut out and colored to make the water egrets more visible. Thin sections are prepared with a microtome which are then examined under a microscope 30 (at 200 X) and the size of the egrets is measured. Normally, four discs are prepared for each test tube, so that the average size of the egrets is calculated from forty individual measurements. In the evaluation of different egret retarders / 35, the relative size of the a.i. ~ ^ grettes is determined by comparing the average size obtained on / J '7.

»1 13 a normal thermoplastic insulating material for high voltages not containing additives delaying egrets.

Various embodiments of the invention will now be described with reference to the concrete examples below. However, it is understood that these examples are given only for the purpose of illustration and do not limit the invention in any way. All parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1

The compositions are prepared by grinding a commercial grade polyethylene ("NA 310") and the egret inhibitor additive (2% by weight) on a black lami-15 with two cylinders at approximately 149 ° C. However approximately 10 minutes, for obtain a homogeneous dispersion. The crepe obtained is then used to prepare the test pieces intended for the tests of electric egret and water egret, by the methods described above.

The results are shown in Table I. All the compositions contain the same ingredients, apart from the egret inhibitor additive shown in Table I, and they include a commercial grade polyethylene having a melt index of about 0.20 at 0.35 g / 3 25 10 min and a density of approximately 0.917 g / cm. The control does not contain an egret inhibitor additive ^ / £. * 14

TABLE I

Test- Additive Time before Egret vette inhibitor deterioration of water n ° of egrets of 50%, min, at (size 5 the test with the two relative) vinyl-tris- needles (2-> 12,700 methoxyethoxy) - ( no dete 0.23 silane riorations) 10 B Y-glycidoxypropyl- 2,800 0.34 trimethoxysilane 1 control (without additive) 80 1 2 vinyltriethoxysilane 30 0, -29 3 ß- (3,4-epoxycyclohexyl) -ethyltrimethoxy-silane 620 0.34 4 dodecanol 127 0.34

The results clearly show the improvement of the properties, as regards both the ai-20 grettes of water and the electric egrets, in the compositions prepared according to the invention. Thus, by comparing test pieces A and B according to the invention and test pieces 1 to 4, foreign to the invention, the improvement can easily be seen. By comparing test piece A 25 with the control, test piece 1, we see the great improvement in properties obtained with vinyl-tris- (2-methoxy-ethoxy) -silane. Likewise, the comparison of test piece A and test piece 2 shows the importance of using a silane containing an electron donor atom in the chain of groups attached to the silicon atom. The comparison of test pieces A and B shows the advantage / of using three electron donor radicals attached / to the silicon atom.

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EXAMPLE II

In the same way as in Example I, a number of organic compounds are evaluated as egret inhibitor additives. In all cases, the additive 5 is incorporated into the polyethylene at a concentration of 1.5%. The results of the electric egret / and water egret tests are shown in Table II.

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The silanes tested demonstrate superior resistance to both water and electric egrets, in the case of alkane-alkoxyl substituted silanes (test tubes 6, 9, 10, 14, 22 and 23), as can be seen by comparing inter alia the silane pairs of samples 6 and 7, 9 and 11 and 13 and 14. It therefore appears that there is an optimal number of alkoxyalkoxyl substituents (compare samples 6, 9 and 10). The effect of a vinyl substituent, in comparison to an alkyl or aryl substituent, is demonstrated by the comparison of test pieces 6, 9 and 22. The location of a particular substituent, namely an aryl group, can influence the inhibition properties of the organic compound, as can be seen in test pieces 22 and 23.

Test specimens 24 and 25 show that organic phosphites are effective in inhibiting water egrets as well as electric egrets, while test tube 26 indicates similar effectiveness for an organic titanium compound.

Although the invention relates mainly to the use of silanes, those skilled in the art will understand that it is possible to use other compounds containing / a polyvalent atom such as titanium, tin, phos- / phore and the like.

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Claims (33)

1. Polymer composition having increased resistance to water egrets and electric egrets and characterized in that it comprises a homogeneous mixture of a polymer component and an effective amount of an egret inhibitor water and electric egrets which is an organic compound corresponding to the formula: R2 - Z - Y1 <CnH2n> Y2S6 <B> '· I <* 3> a 10 in which R2 and Rg are similar or different and represent a group Y ^ (cnH2n ^ Y2R6 'C1 to C8 alkyl, C1 to C8 alkoxyl, C1 to C8 acyloxyl, optionally substituted C1 to C8 aryloxyl, optionally substituted C1 to C8 aryl, a hydrogen atom or halogen, an epoxidized radical, a C2 to C8 alkenyl group, a nitrogen radical, a carboxylated radical, a radical with a mercaptan group or an etherified radical, Rg represents a C1 to C8 alkyl group, C1 to C8 alkoxyl, acyloxyl to C, to CQ, optionally substituted Cc to ClQ aryloxyl, * 1 ob lo 20 Cg to Clg aryl optionally substituted t, hydrogen or halogen t atom, epoxy radical, C2 to C8 alkenyl group, nitrogen radical, carboxyl radical, mercaptan group radical or etherified radical, Y and Y2 are similar or different and 25 represent 0, S or N, Z represents Si, Sn, Ti, P or B, a is O or 1 and n is from 1 to 8, said composition containing 0 to 10% by weight of filler. 2. Composition according to claim 1, characterized in that the polymer is polyVX '30 ethylene. / ^ c 21 3. composition according to claim 1, characterized in that R ^, R2 and R ^ each represent a group Y ^^ cnH2n ^ Y2R6 'alkYl' alkoxyl / acyloxyl, aryl or alkenyl, Rg an alkyl or aryl group and and 5 Y2, each an oxygen atom. 4. Composition according to claim 3, „characterized in that Z represents Si and that a = 1. - 5. Composition according to claim 4, characterized in that R ^ represents a vinyl group, 10 R2 and R3 ckun a group Y ^ icnH2n ^ Y9Rg 'Rg a methyl group and that n = 2. 6. Composition according to claim 3, characterized in that R ^ represents a methyl group, R2 and R3 each a group (cnH2n) Y2R6f R6 1111 9rouPe 15 methyl and that n = 2. 7. Composition according to claim 4, characterized in that R ^, R2 and each represent a group Y ^ cnH2n ^ Y2R6f R6 a methyl group and that n = 2. 8. Composition according to claim 4, characterized in that R ^ represents a Y-methacryloxypropyl group, R2 and R3 each a group Υχ (CnH2n) Y2R6 'R6 a methyl group and that n = 2. 9. Composition according to claim 4, * characterized in that represents a phenyl group, r 25 R2 and R3 each a group Yi (cnH2n ^ Y2R6f R6 A 9rouPe "methyl and that n = 2. 10. Composition according to claim 4, characterized in that R ^ represents a vinyl group, R2 and R3 each a group Y ^ (cnH2n ^ Y2Rg 'R6 A 9rouPe 30 phenyl and that n = 2. 11. Composition according to claim 3, characterized in that Z represents P and that a = 0. 12. Composition according to claim 11, characterized in that R ^ and R2 each represent a group 35 Yi ^ cnH2n ^ Y2R6 'R6 an ethyl 9rouPe and that n = 2./7/ f <> 22. * 13. Composition according to claim 11, characterized in that and R £ each represent a group Y, (C H-) Y-R ^, R, a toutyl group (n) and that n 2. 3. n 2n 2 6 o. 14. Composition according to claim 3, 5 characterized in that Z represents Ti and that a = 1. 15. Composition according to claim 14, characterized in that R ^, R2 and Rg each represent a group (CnH2n) Y2Rg / R6 a methyl group and that n = 2. 16. Composition according to one of claims 10 1 to 15, characterized in that it is hardenable or hardened. 17. Method for stabilizing an electrical conductor with polymeric insulation against water egrets and electric egrets, characterized in that an homogeneous mixture of a polymer component and an amount is used as the insulating composition effective of an inhibitor of water egrets and electric egrets which is an organic compound corresponding to the formula î R2 - * - Y1 <CnH2n> Y2R6 (B) <R3> a in which R1, R_ and R , are similar or different and represent a group (cnH2n ^ Y2R6 'C 1-6 alkYl, C 1-6 alkoxyl, C 1-6 acyloxyl, optionally substituted C 1-6 aryloxyl, C 1-6 aryl optionally substituted *. a hydrogen or halogen atom, an epoxy radical, a C 1 -C 4 alkenyl group, a nitrogen radical, a carboxyl radical, a mercaptan group radical or an etherified radical, Rg represents C1 to C8 alkyl, C to C8 alkoxyl, C1 to C8 acyloxyl, C6 to C1S aryloxyl if desired optionally substituted, optionally substituted C6 to C6 aryl, a hydrogen or halogen atom, an epoxy radical, 3. a C6 to C8 alkenyl group, a nitrogen radical, a / 7 / carboxyl radical, a radical with mercaptan group or a / j / / ri · * 23 etherified radical, Y1 and Y2 are similar or different and represent O, S or N, Z represents Si, Sn, Ti, - P or B, a is 0 or 1 and n is 1 to 8. 18. The method of claim 17, 5 characterized in that the polymer is polyethylene. 19. The method of claim 17, charac- ·. teris in that, R2 and R ^ each represent a group Y ^ (cnH2n ^ Y2R6 'al ^ yl, alkoxyl, acyloxyl, aryl or alkenyl, Rg an alkyl or aryl group and Y and Y2, each one an atom of oxygen. 20. The method of claim 19, characterized in that Z represents Si and that a = 1. 21. The method of claim 20, characterized in that Rx represents a vinyl group, R2 and R3 each a group Y ^ (C H ^) Y2Rg 'R6 a 9rouPe m ^ methyl and that n = 2. 22. The method of claim 20, characterized in that R represents a methyl group, R2 and R_ each a group Y, (C) Y_R_, R ,. a methyl group j 1 η zn δ o b 20 and that n = e 2. 23. The method of claim 20, characterized in that R ^, R2 and R ^ each represent a group Y (C H2n) Y2Rg # Rg a methyl group and that n = 2.. 24. The method of claim 20, * 25 characterized in that R ^ represents a group ^ -methacryloxy-. propyl, R2 and R3 each a group Υχ ^ cnH2n ^ Y2R6 'R6 a methyl group and that n = 2. 25. The method of claim 20, characterized in that R ^ represents a phenyl group, R2 and R ^ each a group Y (cnH2n) Y2R6 'R6 A methyl group and that n = 2. 26. The method of claim 20, characterized in that R. ^ represents a vinyl group, R2 and R3 each a group Y (CnH2n) Y2R6 r R6 a phenyl group and that n = 2. / 3 5 27. Method according to claim 19, character - / "\ / * I t) 24 28. The method of claim 27, characterized in that R ^ and R2 each represent a group Yx (cnH2n ^ T2R6 'R6 1111 ethyl group and that n = 2. 29. The method of claim 27, charac-5 terized in that R. ^ and R2 each represent a group - Y (cnH2n ^ Y2R6f R6 a 9rouPe hutyle (n) and that n = 2. 30. The method of claim 19, characterized in that Z represents Ti and that a = 1. 31. The method of claim 30, charac- - 10 terized in that R2 and R3 each represent a group Y ^ (CnH2n) Y2Rg, Rg a methyl group and that n = 2. 32. Method according to claims 17 to 31, characterized in that the insulating composition is hardenable or hardened. 33. Method according to one of claims 17 to 32, characterized in that the insulating composition contains 0 to 10% by weight of filler. 34. Method according to one of claims 17 to 33, characterized in that the insulating composition 20 contains an effective amount of a crosslinking agent, an antioxidant, a plasticizer, a stabilizer and / or d 'an antistatic. 35. Method according to one of claims 17 to ïk, characterized in that the insulating composition * 25 contains an effective amount of pigment or dye, 36. Electrical conductor coated with the composition according to one of claims 1 to 16. Drawings: .............. boards ... XL ....... pcivcs denial ...... 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