Polyolefin composition for cables of medium, high and superhigh voltage, including additive for stabilisation of dielectric strength of benzyl type

FIELD: chemistry.

SUBSTANCE: invention relates to a polyolefin composition with improved dielectric strength of insulation, to a wire or cable, in particular to a cable of middle, high or superhigh voltage, which includes such composition, as well as to application of such composition for production of wire or cable, in particular a cable of medium, high and superhigh voltage. Polyolefin composition contains polyolefin (A) and benzyl derivative (B) of a certain structure. Benzyl derivative (B) is used in the polyolefin composition as an additive for stabilisation of dielectric strength.

EFFECT: additive provides considerable improvement of dielectric strength, possesses good solubility in a polyolefin matrix and low predisposition to migration, and also possesses compatibility with respect to all other components of the polyolefin composition, in particular with cross-linking agents.

21 cl, 6 tbl, 5 ex

 

The present invention relates to a polyolefin composition with improved electrical strength of insulation, wire or cable, in particular to the cable medium, high or extra-high voltage, comprising such a composition and to the use of such compositions for the production of wire or cable, in particular a cable medium, high and extra high voltages.

Standard power cables medium voltage, typically used for voltages from 6 to 36 kV, standard power cables high voltage used for a voltage exceeding 36 kV and power cables high voltage more than 220 kV, include one or more than one conductor in the cable core surrounded by several layers of polymeric materials, including inner semiconducting layer, followed by an insulating layer, and further the outer semiconductor layer. These layers are typically cross-linked. These layers may be added others, such as metal coil or wire protection, shielding layers, and finally, the layer (s) of the outer shell. Layers of the cable are made on the basis of different types of polymer compositions. As the insulating materials currently mainly used cross-linked polyolefins type cross-linked polyethylene low density the property.

A permanent task of the manufacturers of the cables is to increase the electric strength of insulation materials of cables, in particular insulating material of the cables, in order to achieve the best reliability, or the development of new cable designs, in which the insulation will be exposed to a higher load. Defects in isolation determine the minimum insulation thickness and, consequently, the maximum rated voltage to be applied to the cable. It is known that to achieve the high reliability of cable structures high voltage reduce the amount of impurities in the insulating material. At present, however, to isolate the use of very pure materials, and improving electrical insulation strength by reducing the impurity content is associated with a significant increase in value.

It is also known the use of supplements, namely, so-called additives for stabilizing electric strength, to increase the electrical strength of insulating materials cable. For example, in the document US 3482033 described the use of a mixture of non-volatile hydrocarbon oils with a high content of aromatic compounds or reference to ha, low-melting hydrocarbons with active additives for the stabilization of the electric strength, such as POLYHALOGENATED or as ematicheskie connection containing nitrogroup.

In addition, known additives for the stabilization of the electric strength of document WO 01/08166. This document disclosed the voltage regulators on the basis of benzophenone as the main molecule, substituted alkyl, aryl, alkoxy and arroxyjoype.

However, there is a need for additives to stabilize electric strength, which improves the electrical insulation strength polyolefin compositions used for cable insulation medium/high/ultra-high voltage. Such additives for the stabilization of the electric strength, generally have low ionization potential to reduce the energy of high-energy electrons and, therefore, effectively improve dielectric strength (see, for example ..Ashcraft, R. Eichhorn, and S.R.G., "Laboratory Studies of Treeing in Solid Dielectrics and Voltage Stabilization of Polyethylene", presented at the I.E.E.E. International Symposium on electrical insulation, Montreal, Canada, 1978).

At the same time, the connection must be soluble in the polyolefin, generally, cross-linked polyethylene used as the polymer matrix in the composition, and, in addition, must have a low propensity to migrate, so that the loss of substances in the insulation material over time was as little as possible.

Further preference is sustained fashion, as usual insulating materials are cross-linked polyolefins, additives for the stabilization of the electric strength should be as compatible as possible with the commonly used cross-linking agents such as organic peroxides, in order, on the one hand, not to have a negative impact on the process of cross-stitching, and, on the other hand, additives for the stabilization of the electric strength must not be reactive or decaying, which can reduce their effectiveness or even, in the worst case, to make them inactive. Of course, additives for the stabilization of the electric strength must be compatible with respect to all other components of the polyolefin composition.

Thus, the present invention is to provide a polyolefin composition containing an additive for stabilizing the electric strength polyolefin compositions, in particular for use as an insulating composition in the cable medium/high/ultra-high voltage, possessing the above properties. In particular, additive for stabilizing the electric strength provides a significant improvement in electric strength, also preferably has a high solubility in polyolefin mA is the matrix and a low propensity to migrate, and more preferably is compatible with respect to all other components of the polyolefin composition, in particular with cross-linking agents.

Unexpectedly found that the above problems can be achieved using a polyolefin composition, in both cases, the concentrated mixture contains benzyl derivative, and by applying the specified benzyl arbitrary, which contains one or more than one Deputy on the phenyl groups, benzyl molecules containing hydrocarbonous group, as an additive for stabilizing the electric strength.

Thus, in the present invention proposed a polyolefin composition comprising (1) a polyolefin (A),

(2) benzyl derivative (B)comprising, preferably consisting of structural units of the following formula (I):

where one or more than one carbon atom in the phenyl ring to which(th) attached residues R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 may(ut) to represent the heteroatom(s), so(s) as N, in this case, the corresponding residues R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 is absent;

R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 independently of one another are hydrogen or hydrocarbon group which may contain heteroatoms;

or at IU is E. two of the above R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 together with the ring atoms of the ring system of the formula (I), to which they are attached, form an additional aromatic or non-aromatic ring condensed with a ring system of formula (I), and where the ring system of the formula (I) with the specified at least one more condensed ring may also contain from one to eight substituents, R1' to R8', each of which is independently selected from these same groups as R1 - R10, and

n=from 2 to 9,

provided that

(i) at least one of the R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10, or, if there is at least one of the R1' - R8' represents a hydrocarbon group which may contain one or more than one heteroatom.

The term "hydrocarbon group" means any Deputy consisting of carbon atoms and hydrogen, irrespective of the degree of saturation, i.e. alkyl groups, alkeline group, alkyline group and aromatic group consisting of C and N. If you specify that the hydrocarbon group may contain heteroatoms, these atoms different from C and H represent Si, N, P, O or S, typically N or O.

Found that the use of these compounds as additives for stabilizing the electric strength results in polyolefin compositions with things is to promote better electrical insulation strength. Improve electrical insulation strength can be evaluated by high values of molar stability, measured as described below. In addition, the compounds have good solubility in the polyolefin matrix and a low propensity to migrate, and are compatible with other components of the polyolefin composition, in particular with cross-linking agents.

If any of the above R1, R2, R3, R4, R5, R6, R7 or R8, and if there is any of R1'-R8' represents a hydrocarbon group which may contain one or more than one heteroatom attached to the aromatic ring of the compounds of formula (I), preferably, the specified hydrocarbon group did not contain atoms N in the alpha position.

Preferably, the amino taking into account the conditions (i) may be contained in the specified hydrocarbon group, which is at least one of R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10, or, if there is at least one of the above R1'-R8'. Preferably the amino group is a tertiary amino group. Tertiary amino group, in the description below referred to as tert-amino group is an amino group containing three hydrocarbon substituent, which may contain one or more than one heteroatom on atom n

In preferred in which lewinii specified at least one of the above-mentioned R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10, or, if there is at least one of the R1'-R8', which given the conditions (i) represents a hydrocarbon group which may contain heteroatoms and which contains an amino group selected from the groups-N(R11)(R12) and-Ar-N(R11)(R12), where R11 and R12 independently of one another are hydrocarbon groups that may contain one or more than one heteroatom, and ar represents an aryl group which may contain one or more than one heteroatom.

In the preferred embodiment of the specified at least one of the above-mentioned R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10, or, if there is at least one of the R1'-R8' represents a hydrocarbon group provided that (i) and is selected from -0(R13), and-Ar-0(R13)where R13 represents H or a hydrocarbon group which may contain one or more than one heteroatom, and ar represents an aryl group which may to contain one or more than one heteroatom.

Preferably, in the compounds with the structural units of formulas (I) all atoms in phenyl or naftalina rings, which are attached to the remainder of R1-R10 are carbon atoms.

In addition, preferably, R11, R12 and R13 independently represent aryl or alkyl group, more preferably an alkyl group, and more preferably of nerazvit the military alkyl group, which may contain or not contain a functional group on the end opposite the corresponding ring atom attached to the remainder. Group, if present, is preferably-CH=CH2, halogen, hydroxyl, carboxylic acid or halogenoalkanes group.

R11, R12 and R13 independently preferably contain at least 1 or 2 carbon atoms, more preferably at least 4 carbon atoms, more preferably contain at least 5 carbon atoms, and most preferably at least 6 carbon atoms.

Examples of such preferred embodiment of the benzyl derivative (B)comprising -0(R13)presented 4-methoxybenzyl and 4-hydroxybenzyl.

In addition, preferably, R11, R12 and R13 independently contain not more than 50 carbon atoms, more preferably not more than 30 carbon atoms, still more preferably not more than 20 carbon atoms, and most preferably not more than 16 carbon atoms.

Ah preferably represents a substituted or unsubstituted, preferably unsubstituted phenyl group.

The number n in the formula (I) is preferably from 2 to 6, more preferably 2 or 3, and still more preferably equal to 2.

In addition, preferably compounds comprising or consisting of the structural units fo the formula (I), do not contain halogen substituents or substituents including halogen atoms.

In addition, it is preferable that the structural units of the formula (I) one or two of R1-R10, or, subject to the availability of R1'-R8' is or are hydrocarbon groups, including the amino group in any of the embodiments described above, and the remaining of R1-R10 or, if R1'-R8' are N.

In such cases, where two or more than two of R1-R10 or-if available-R1'-R8' are described hydrocarbon groups, preferably to these hydrocarbon groups were separated by at least one additional ring atom, for example, are located in different phenyl groups, or are in meta-position relative to each other, if the two groups attached to the same phenyl group in formula (I).

In an additional preferred embodiment of the benzyl derivative (C) comprises, or consists of structural units of the formula (I)in which R3 to R8 independently represent a group-N(R11)(R12), R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 represents H, where R11 and R12 have the meaning set forth in any of the above embodiments.

An example of such a preferred embodiment of the benzyl derivative (C) is a 4,4'-bis(dioctylamine)benzyl.

In an additional preferred embodiment of gasoline is inoe derivative (B) comprises or consists of structural units of the formula (I), where R3 and R8 represent a group-N(R11)(R12), R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 represent H, where R11 and R12 have the meaning set forth in any of the above embodiments.

An example of such a preferred embodiment of the benzyl derivative (C) is a 4-dioctylamine.

In yet another preferred embodiment of the benzyl derivative (B) comprises or consists of structural units of the formula (I)where R3 and R8 independently represent a group -0(R13), R1, R2, R4, R5, R6, R7, R9 and R10 represent H, where R13 has the meaning given in any of the above embodiments.

Examples of such preferred embodiment of the benzyl derivative (C) represent the pair-anisil, 4,4'-dihydroxybenzyl, 4,4'-geodecisions and 4,4'-diodes-10-aniloxes.

In yet another preferred embodiment of the benzyl derivative (B) comprises or consists of structural units of the formula (I)where one of R3 and R8 is a group -0(R13), R1, R2, R4, R5, R6, R7, R8, R9 and R10 represent H, where R13 has the meaning given in any of the above embodiments.

Examples of such preferred embodiment of the benzyl derivative (B) are 4-hydroxybenzyl, 4-dodecyloxybenzoyl, and 4-undec-10-aniloxes.

Preferably, in all the above embodiments of the benzyl derivative (consisted of structural units, described in the specific embodiments. However, in all cases, when the aromatic system(s) of formula (I) contains at least two Deputy, then it is possible that the structural units of any of the above embodiments moved into oligomeric structures to increase molecular weight.

In addition, it is possible and is within the scope of the invention connection connection (In) to one or more than one additional component of the polyolefin composition according to the invention, for example joining polyolefin (A).

The specified connection can be made by copolymerization of comonomers containing additives for stabilizing electric strength, and "regular" Monomeric units, such as polyolefin (A), or by inoculation of suitable compounds additives for the stabilization of the electric strength to the polymer skeleton.

Preferably, the compound (C) is present in the composition in an amount of from 0.001 to 10 wt.%, more preferably from 0.01 to 5 wt.%, even more preferably from 0.05 to 4 wt.%, even more preferably from 0.1 to 3 wt.% and most preferably from 0.1 to 2 wt.%. More preferred ranges for compound (C)represented in the composition ranges from 0.05 to 3 wt.%, from 0.05 to 2 wt.% or from 0.05 to 1.5 wt.%.

The polyolefin (A) can the t be any polyolefin material, suitable for use in the production of a layer of a cable, preferably a layer of a power cable, more preferably the insulation layer of the power cable.

The polyolefin (A) preferably comprises or consists of polyethylene or polypropylene. When referred to in this document, the term "polymer, for example polyethylene, should be understood as Homo - or copolymer, for example, ethylene Homo - and copolymer.

If the polyolefin (A) comprises or consists of polyethylene, the polymer is preferably obtained using the method under high pressure or low pressure in the presence of a catalyst, such as chromium catalyst of the Ziegler-Natta or catalyst with a single center of polymerization, resulting in obtaining or odnomodovogo, or multimodal polyethylene.

If the polyolefin (A) comprises or consists of polypropylene, the polypropylene can be odnodolnym or multimodal propylene Homo - or copolymer, and/or heterophase polypropylene.

In addition, if the polyolefin (A) comprises or consists of polypropylene, it preferably should have a P2(the flow rate of the melt) (230°C, 2,16 kg) from 0.001 to 25 g/10 minutes

In the preferred embodiment the polyolefin (A) comprises or consists of the ethylene Homo - or copolymers. In this case, the ethylene sprinklers the measures which is preferred, includes from 0.001 to 50 wt.%, more preferably from 0.1 to 40 wt.%, even more preferably less than 35 wt.%, even more preferably less than 30 wt.%, and most preferably less than 25 wt.% one or more than one of the co monomer.

Preferably, the density of the ethylene Homo - or copolymer does not exceed 0,860 g/cm3.

Moreover, preferably the density of the ethylene Homo - or copolymer does not exceed 0,960 g/cm3.

P2(the rate of melt flow) (of 2.16 kg, 190°C.) of the ethylene Homo - or copolymer is preferably from 0.01 to 50 g/10 min, more preferably from 0.1 to 20 g/10 min, even more preferably from 0.2 to 15 g/10 min, and most preferably from 0.2 to 10 g/10 minutes

In addition, it is preferable that the polyolefin (A) included or consisted of polyethylene, which was obtained using the method under high pressure using free radical polymerization, which leads to the result, it is preferable to obtain low density polyethylene (LDPE). The polymerization is generally carried out at pressures of from 120 to 350 MPa and temperatures from 150 to 350°C.

LDPE may be ethylene homopolymer or copolymer.

As co monomer in the ethylene copolymer can be used non-polar alpha-olefins, either separately or in addition to catfish the numbers of other types. These alpha-olefins may also include unsaturated communication, such as the polyunsaturated comonomers, such as diene.

Preferred non-polar alpha-olefins are3-C20alpha-olefins, preferably as comonomers used With3-C10alpha-olefins, such as propylene, 1-butene, 1-hexene, 4-methyl-1-penten, styrene, 1-octene, 1-nonen, polyunsaturated comonomers, preferably8-C14unpaired diene, such as 1,7-octadiene, 1,9-decadiene, 1,11-dodecadien, 1,13-tetradecane, or any mixture. As additional examples of unsaturated comonomers may be mentioned diene, such as 7-methyl-1,6-octadiene, 9-methyl-1,8-decadiene or mixtures thereof.

It is also possible to use polar comonomers, possibly in conjunction with non-polar alpha-olefin of the comonomers. Preferably, as the polar Monomeric units use compounds containing hydroxyl groups, CNS groups, carbonyl groups, carboxyl groups, esters and ethers.

Even more preferably, the polar monomer units selected from the group alkylacrylate, alkyl methacrylates, and vinylacetate or mixtures thereof. Preferably the comonomers are selected from C1-C6alkylacrylate,1-C6-alkyl methacrylates and vinyl acetate is. Even more preferably, the polar copolymer includes ethylene copolymer with1-C4-alkyl, such as methyl, ethyl, propyl or butylacrylate or vinyl acetate, or any mixture.

If the units of the polar co monomer is present in the polyolefin (a), it is preferable that the number was the values defined above and below.

If the copolymer is LDPE, it is preferred to include from 0.001 to 50 wt.%, more preferably from 0.1 to 40 wt.%, even more preferably less than 35 wt.%, even more preferably less than 30 wt.%, and most preferably less than 25 wt.% one or more than one of the co monomer.

The polyolefin (A) is preferably cross-linked. Cross stitching can be done, for example, by the addition of cross-linking agent in the composition or by incorporating cross-stitched groups in the polyolefin (A).

In the preferred embodiment of the polymer composition of the present invention further includes a cross-linking agent.

In the context of the present invention a cross-linking agent is defined as any compound capable of generating radicals initiating the reaction cross-stitching. Preferably, cross-linking agent contains at least one link-o-O and the at least one link-N=N-.

Cross-linking agent, such as peroxide, is preferably added in an amount less than 10 wt.%, more preferably from 0.1 to 5.0 wt.%, even more preferably from 0.1 to 3.0 wt.%, or more preferably from 0.15 to 2.6 wt.%, on the basis weight cross-stitched polymeric composition.

As examples of peroxides as cross-linking agents, do not limit the present invention can lead di-tert-AMYLPEROXY, 2,5-di(tert-BUTYLPEROXY)-2,5-dimethyl-3-hexyne, 2,5-di(tert-BUTYLPEROXY)2,5-dimethylhexane, tert-butylcumylperoxide, di(tert butyl)peroxide, dicumylperoxide, bis(tertBUTYLPEROXY)benzene, butyl-4,4-bis(tert-BUTYLPEROXY)-valerate, 1,1-bis(tert-BUTYLPEROXY)-3,3,3-trimethylcyclohexane, tert-butyl peroxybenzoate, Dibenzoyl peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 1,1-di(tert-BUTYLPEROXY)cyclohexane, 1,1-di(traceminerals)cyclohexa, or any mixtures thereof.

Preferably, the peroxide is selected from 2,5-di(tert-BUTYLPEROXY)-2,5-dimethylhexane, di(tertBUTYLPEROXY)benzene, dicumylperoxide, tert-butylcumylperoxide, di(tert-butyl)peroxide, or mixtures thereof. Most preferably, the peroxide is dicumylperoxide.

Preferably, cross-linking was carried out by introducing a cross-linking agent, such ka is peroxide, in any of the above embodiments, in the composition.

However, cross-linking can also be accomplished using the hydrolyzable Milanovich groups that may be present in the polyolefin (A). Thus, the polyolefin (A) may also include or consist of cross-stitched polyolefin containing hydrolyzable silane groups. Hydrolyzable silane groups are usually cross-stitched using the condensation catalyst in the presence of water.

Hydrolyzable silane groups can be introduced into the polyolefin by copolymerization, for example, ethylene monomers with comonomers containing silane groups, or by inoculation, i.e. by chemical modification of the polymer by adding Milanovich groups, mainly in radical reactions. Both methods are well known in the prior art.

If the polyolefin (A) comprises or consists of the unsaturated polyolefin, i.e. polyolefin containing a double carbon-carbon connection, it is preferable that the polyolefin characterized by the total number of carbon-carbon double bonds/1000 carbon atoms, is 0.1 or more, more preferably 0.2 or more, more preferably 0.3 or more, and most preferably more than 0,37.

The upper limit of the content of the carbon-carbon double tie the th, present in the polymer is not limited and may preferably be less than 5,0/1000 carbon atoms, preferably less than a 3.0/1000 carbon atoms, or more preferably less than 2.5/1000 carbon atoms.

When used in combination with unsaturated polyolefin, the term "total number of carbon-carbon double bond" refers to the double bonds originating from the vinyl groups, vinylidene groups and TRANS-vinilovyh groups. The number of double bonds of each type measured in accordance with the specified in the experimental part.

Introduction the total number of double carbon-carbon bonds in the polyolefin component allows you to improve cross-stevenote.

The total number of vinyl groups is preferably exceed 0.02/1000 carbon atoms, more preferably greater than 0.05/1000 carbon atoms, even more preferably greater than 0,08/1000 carbon atoms, and most preferably is more than 0.11/1000 carbon atoms.

Preferably, the total content of the vinyl groups is lower than 4.0/1000 carbon atoms.

Preferred unsaturated polyolefin (A) is an unsaturated polyethylene or unsaturated polypropylene. More preferably, the unsaturated polyolefin is an unsaturated polyethylene and more preferably unsaturated Homo - what do copolymer or even more preferably unsaturated Homo - or copolymer of LDPE.

Preferably, the unsaturated polyolefin is obtained by copolymerization of at least one olefinic monomer with at least one polyunsaturated co monomer.

In the preferred embodiment, the polyunsaturated comonomer consists of unbranched carbon chain containing at least 8 carbon atoms and at least 4 carbon atoms between the non-conjugate double bonds, where at least one of them is the limit.

Siloxanes having the following formula:

CH2=CH-[Si(CH3)2-O]n-Si(CH3)2-CH=CH2where n=1 or more

you can also use polyunsaturated co monomer. As an example we can mention diphenylsiloxane, such as alpha, omega-diphenylsiloxane.

In addition to polyunsaturated co monomer perhaps you can use the optional comonomers, preferably nonpolar3-C20alphaolefins comonomers, more preferably3-C10alphaolefins comonomers without additional ninasimone, such as propylene, 1-butene, 1-hexene, 4-methyl-1-penten, styrene, 1-octene and/or 1-nonen, polar comonomers, or any mixtures thereof.

It is also possible to use polar comonomers, possibly in combination with non-polar alphaolefins the co monomer(s). Preferably, as is e-polar Monomeric units use joins containing a hydroxyl group, alkoxygroup, carbonyl groups, carboxyl groups, esters and ethers.

Even more preferably, the polar monomer units selected from the group alkylacrylate, alkyl methacrylates and vinylacetate or mixtures thereof. In addition, preferably, the comonomers are selected from C1-C6alkylacrylate, C1-C6the alkyl methacrylates, and vinylacetate. Even more preferably, the polar copolymer units include ethylene copolymer with1-C4the alkyl, such as methyl, ethyl, propyl or butyl acrylate or vinylacetate, or any mixtures thereof.

If polar comonomer units are present in the polyolefin (a), preferably the content should be the same as defined above.

When receiving the unsaturated polyolefin, such as unsaturated polyethylene using the method under high pressure polymerization, as a rule, carried out at pressures in the range from 120 to 350 MPa and at temperatures in the range from 150 to 350°C.

The polyolefin can be unimodal or multimodal, e.g. bimodal.

In the preferred embodiment the polyolefin (A), as polyethylene or preferably unsaturated polyethylene contains at least 50 wt.% ethylene Monomeric units.

Preferred is polyethylene is h or preferably unsaturated low-density polyethylene.

In addition to the components of the polyolefin (a) and aromatic compounds (C), the polymer composition may contain additional components, which may be, for example, another polymer of any type.

In one embodiment the polymer composition according to the invention further includes a polar copolymer (C).

Polar copolymers (C) are preferably olefinic copolymers, more preferably propylene or ethylene copolymers containing polar comonomers, preferably from defined above.

Preferably, the polymer composition further comprises an inhibitor of premature polymerization. In the context of the present invention the inhibitor premature polymerization" means a compound that reduces the occurrence of premature polymerization during extrusion of the polymer composition, at temperatures of conventional extrusion, compared to the same polymer composition, extruded without the specified connection. In addition to the properties of inhibiting premature polymerization inhibitor premature polymerization can have additional effects, such as stimulation, i.e. the improvement of the characteristics of cross-stitching during the stage of cross-stitching.

Preferred inhibitors pricefrom is authorized polymerization are unsaturated dimers of aromatic alpha-methylalanine monomers, such as 2,4-diphenyl-4-methyl-1-penten, substituted or unsubstituted diphenylamine, derivatives of quinone, hydroquinone derivatives, monofunctional vinylstyrene esters and ethers, monocyclic hydrocarbons containing at least two or more than two double bonds, or mixtures thereof. More preferably, the inhibitor premature polymerization are selected from 2,4-diphenyl-4-methyl-1-pentene, substituted or unsubstituted diphenylethylene, or mixtures thereof.

Preferably, the amount of inhibitor premature polymerization is in the range of 0.005 to 1.0 wt.%, more preferably in the range from 0.01 to 0.8 wt.%, on the basis of the mass of the cross-stitched polyolefin composition. More preferred ranges are from 0.03 to 0.75 wt.%, from 0.05 to 0.70 wt.% and from 0.05 to 0.50 wt.% on the basis weight cross-stitched polyolefin composition.

The polymer composition may contain additional additives, such as antioxidant(s), stabilizer(s), processing AIDS and/or the stimulator(s) of cross-stitching. As an antioxidant it is possible to mention steric zatrudnienie or polystryrene phenols, aromatic amines, aliphatic steric employed amines, organic phosphates, sulfur containing compounds, and mixtures thereof.

Typical stimulants Shiva the Oia may include connections, containing at least 1, preferably at least 2 unsaturated groups such as vinyl or allyl groups, such as aliphatic or aromatic compound, complex, or ethers, or ketones, which contain at least 1, preferably at least 2 unsaturated group(s), such as cyanurate, isocyanurate, phosphate, ortho-formate, aliphatic or aromaticheskie ethers, or allilaire benzene tricarboxylic acid. Examples of complex or simple esters and ketones are compounds selected from the General group of diacrylates, triacrylate, tetraacrylate, cialiscanadaow, triallylisocyanurate, or any mixtures thereof, containing, for example, treelistener, triallylisocyanurate, and di-, tri - or Tetra-acrylates.

As additional additives may be mentioned additives, which impart flame-retardant properties, sinks acid, inorganic fillers, preferably selected from carbon or a refractory filler, inhibitors water tryinga and other additives to stabilize the electric strength.

If you are using an antioxidant, possibly a mixture of two or more than two antioxidants, then the added amount may be in the range of 0.005 to 2.5 wt.% based on the weight of the polymer composition.

As a rule, if the track uses the I polyethylene, it is preferable to add an antioxidant(s) in an amount of 0.005 to 1.5 wt.%, more preferably from 0.01 to 1.2 wt.%, even more preferably from 0.04 to 0.80 wt.% based on the weight of the polymer composition.

Similarly, if the composition is polypropylene, it is preferable to add an antioxidant(s) in an amount of 0.005 to 2 wt.%, more preferably from 0.01 to 1.5 wt.%, even more preferably from 0.05 to 1 wt.% based on the weight of the polymer composition.

Extra(s) additive(s) may be present in an amount of from 0.001 to 5 wt.%, more preferably 0.005 to 3 wt.%, even more preferably 0.005 to 2 wt.% based on the weight of the polymer composition. Refractory additives and inorganic fillers may be present in large quantities.

When used for semiconductor layers, the composition may include carbon soot in the usual quantities, preferably in quantities of from 10 to 60 wt.%, more preferably from 20 to 50 wt.%.

P2(of 2.16 kg, 190°C.) of the polymer composition is preferably from 0.01 to 50 g/10 min, more preferably from 0.1 to 20 g/10 min, and most preferably from 0.2 to 10 g/10 min, in the absence of inorganic filler.

The polyolefin (a) and the compound (C), possibly in combination with one or more than one additional additive, discuss what has been learned above, can be mixed by any conventional means to produce in the resulting polymer composition according to the invention.

The polymer composition preferably contains a double carbon-carbon links in the amount of at least 0,1/1000 carbon atoms, preferably at least 0,2/1000 carbon atoms, or more preferably between 0.30/1000 carbon atoms. The upper limit of the content of the double carbon-carbon bonds present in the polymer composition is not limited and may preferably be 5.0/1000 carbon atoms, preferably below 3.0/1000 carbon atoms, or more preferably less than 2.5/1000 carbon atoms.

The total number of double bonds in the stitching polymeric compositions based on vinyl, vinylidene and TRANS-vinilovyh groups/1000 carbon atoms of the component (a) and/or any additional components in the polymer composition containing such groups.

C-C double bonds present in the polymer composition include vinyl groups, and the total number of these vinyl groups is, in order of preference, at least 0,02/1000 carbon atoms, at least 0,05/1000 carbon atoms, at least 0,08/1000 carbon atoms, at least 0,10/1000 carbon atoms or at least 0,11/1000 carbon atoms.

The upper limit of the total content of the vinyl g is PP, present in the polymer composition is typically in the order of preference, up to 4.0/1000 carbon atoms, up to 3.0/1000 carbon atoms, up to 2.5/1000 carbon atoms, or up to 2.0/1000 carbon atoms.

Accordingly, the total content of vinyl groups, subject to availability, contributing to the total number of C-C double bonds contained in the polymer composition. The total number of vinyl groups may also be formed from any of the above-mentioned vinyl groups in the polymer and, subject to the availability of other additives, such as stimulators, inhibitors of premature polymerization or other additional additives.

Of the polymeric composition described above, it is possible to obtain a cross-linked composition by mixing a cross - linking agent followed by treatment under conditions of cross-stitching, thereby increasing the degree of cross-stitching. Cross stitching can be performed by processing at elevated temperature, for example at a temperature at least in the range of 150-160°C. When using a peroxide crosslinking, mainly initiated by raising the temperature to the decomposition temperature of the corresponding peroxide. Decomposition of peroxide radicals are formed. These radicals then initiate the crosslinking reaction.

The total content of additives in polyolefin compositions posovremeni is, typically, 0.05 to 15 wt.%, preferably 0.1 to 12 wt.%, more preferably 0.1 to 10 wt.%.

Of the polymeric compositions of the present invention can be obtained layered product, where at least one layer includes a specified polymer composition. When initiating cross-stitching receive cross-linked multilayer product. Preferably the layered product (either custom made or not) is a cable, preferably a power cable.

In the context of the present invention, power cable means a cable that transmits energy at any voltage. The voltage applied to the power cable may be an alternating (AC), direct (DC) or transient (pulse).

In the preferred embodiment of the multilayer product is a power cable, with applied voltages above 1 kV. In other preferred embodiments, the power cable is produced according to the present invention can withstand 6 kV or higher.

Power cable can be obtained using the method in which the composition of the present invention, possibly in combination with a cross-linking agent is applied to the substrate by extrusion. In this extrusion process, the sequence of mixing the components in the composition may vary, as explained below.

In accordance with a preferred embodiment of the poly is Latin (A), possibly in combination with other polymer components, the compound (C) are mixed with each other and possibly with other additives, either in solid pellets or powder of different polymer components, or by mixing the melt with subsequent formation of pellets from the melt.

Accordingly, in the case of cross-linking agent, preferably peroxide, and possibly inhibitor premature polymerization, and stimulants cross-stitching add to the granules or powder in the second stage. In another case, the inhibitor premature polymerization and/or stimulator of stitching can be added in the first stage together with additives. The obtained granules are loaded into the extruder, for example an extruder for the production of cables.

In accordance with yet another preferred embodiment, instead of the two-stage method, the polyolefin (a) and any other polymer component(s) of the composition, preferably in the form of granules or powder, the compound (b) and optionally additional additives, cross - linking agent and/or inhibitor premature polymerization is added to the extruder-mixer, single-screw or twin-screw extruder. Preferably, the extruder-mixer operates with careful temperature control.

In accordance with another preferred GP is emeniem mixture of the component (C) together with all other additives, i.e. including the antioxidant(s) and cross-linking agent and possibly inhibitor premature polymerization and/or additional additives, such as a stimulator of cross-stitching add to the granules or powder, made of polyolefin (A) and, possibly, other polymer components.

In accordance with another preferred embodiment of the granules made of polyolefin (a) and compounds (B)may additionally contain other polymer components and optional additives, receive at the first stage, for example by mixing of the melt. These granules obtained by melt mixing, and then loaded into the extruder for the production of cables. Maybe next cross-linking agent and optional inhibitor premature polymerization and/or stimulator of cross-stitching serves to bunker, bunker, or directly to the extruder for the production of cables and possibly together with additional polymeric components, if they are not added in the first stage. Alternatively, cross-linking agent, inhibitor premature polymerization and/or stimulator of cross-stitching add to the granules before downloading these pellets in the extruder for the production of cables, or only cross-linking agent is added immediately before nourishing the hopper, to the feed hopper or directly into the extruder for the production of cables, if all other components are already added in the previous stages.

In accordance with another preferred embodiment of pellets, derived from the polyolefin (a) and any other additional polymer component(s), without any additional components are loaded into the extruder. Further, the component (b) and, possibly, the antioxidant(s), cross-linking(e) agent(s), and possibly inhibitor premature polymerization, possibly in combination with additional additives, such as a stimulator of cross-stitching, or download in nutrient hopper or directly into the polymer melt within the extruder for the production of cables. Compound (In) can be added at this stage instead, together with antioxidants, cross-linking agent and other optional additives used. Alternatively, one or more than one of these components, i.e. cross-linking agent, inhibitor premature polymerization, the stimulator stitching, antioxidant(s), compound (V) or a mixture of these components add to the granules before loading the data granules in an extruder for the production of cables, i.e. components that are not yet present in the loaded granules, but which must be present in the cable, neobhodimosti at any stage of the extrusion of the cable.

In accordance with another preferred embodiment of the compound (In) can also be entered in the fallopian mixture containing at least a polymer matrix in an amount of 50 wt.% or more, the compound (In). Compound (In) can also be present in the granules and the antioxidant(s), cross-linking agent, etc. can be added to one or more than one uterine mixture.

This Royal blend then add or mixed with the polyolefin (A) and any additional polymer components and then treated using a known method of obtaining products such as power cable.

Upon receipt of the power cable by extrusion of the polymer composition can be applied to the metallic conductor and/or at least one covering layer, such as a semiconductor or insulating layer. Typical extrusion conditions mentioned in document WO 93/08222.

Mixing can be performed using any method of mixing known from the prior art, including extrusion of the final product in a single screw extruder or a kneading machine.

The present invention also relates to a wire or cable, comprising the polyolefin composition in any of the above embodiments.

In the preferred embodiment of the invention relates to a cable medium, high and swerv the high voltage, includes one or more than one conductor in the cable core, an inner semiconducting layer, followed by an insulating layer, and further the outer semiconductor layer, where at least one of these layers, preferably the insulating layer includes a polyolefin composition described above.

The term "conductor" in this document means a conductor comprising one or more than one wire. In addition, the cable may include one or more than one such Explorer. Preferably the conductor is an electrical conductor.

One or more than one layer can be cross-linked.

In addition to the semiconductor and insulating layers in the cable medium, high or extra high voltage may be additional layers, such as metal tape or wire protection, screen(s) and, finally, the layer (s) of the outer winding.

The invention also relates to the use of polyolefin compositions according to the invention in any of the above embodiments for the production of layers of wire or cable, preferably the layer, more preferably the insulating layer of the cable medium, high or extra-high voltage.

The polyolefin composition of the present invention, including the above-mentioned additive for stabilizing the electric about the particular voltage, particularly superior in terms of electrical strength and thus achieves excellent molar region of stability, measured in the following method of testing electrical Taringa. This behavior makes the polyolefin compositions of the present invention very suitable for use as the insulating layer of the cable medium, high or extra-high voltage.

The preferred embodiment of this polyolefin compositions are compositions comprising the above components (A), the polyolefin (a) and (b) in any of the above embodiments and amounts.

Finally, the invention relates to the use of the benzyl derivative (B) as an additive to stabilize the electric strength of the polyolefin composition, where the specified benzyl derivative (C) comprises, preferably consists of structural units of the following formula (I):

where one or more than one carbon atom in the phenyl rings, which are attached to the residues R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 may also be a heteroatom, such as N, in this case, the corresponding residues R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 will not be present;

R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 independently represent hydrogen or a hydrocarbon group that can in order to keep heteroatoms;

or at least two of the above R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 together with the ring atoms of the ring system of the formula (I), to which they are attached, form an additional aromatic or non-aromatic ring condensed with a ring system of formula (I), and where the ring system of the formula (I) with the specified at least one more condensed ring may carry from one to eight substituents, R1'-R8', each of which is independently selected from these same groups, as R1-R10; and

n=2-9,

provided that

(i) at least one of the R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10, or, if there is at least one of the R1'-R8' represents a hydrocarbon group which may contain heteroatoms.

To illustrate the present invention, the following examples.

Examples

1. Ways to measure

a) the flow Rate of the melt

The rate of flow of the melt (P) determined according to ISO 1133 and is expressed in g/10 min. P is a measure of the fluidity and therefore the ability to process the polymer. The higher the flow velocity of the melt, the lower the viscosity of the polymer. P is determined at 190°C. for polyethylene and can be determined at different loadings such as 2,16 kg (P2) or 21.6 kg (P21). P is determined at 230°C. for polypropylene.

b) Of the definition of the number of double bonds

The method for determining the number of double bonds/1000 carbon atoms based on the method of ASTM D3124-72. In this way a detailed description of the definition vinylidene groups/1000 carbon atoms is provided on the basis of 2,3-dimethyl-1,3-butadiene. The procedure of sample preparation was also used for determination of the vinyl groups/1000 carbon atoms, vinylidene groups/1000 carbon atoms and TRANS-vinilovyh groups/1000 carbon atoms in the present invention. However, to determine the extinction coefficient for these three types of double bonds used the following compounds: 1-the mission for the vinyl, 2-methyl-1-hepten for vinylidene and TRANS-4-mission for TRANS-vinilovyh, followed by the method described in the ASTM D3124, section 9.

The total number of double bonds were analyzed using IR spectrometry and expressed as the amount of vinyl bonds /1000 carbon atoms, vinylidene links/1000 carbon atoms and TRANS-vinilovyh links/1000 carbon atoms, respectively.

Extruded thin film with a thickness of 0.5-1.0 mm was Measured actual thickness. Analysis by infrared spectroscopy with Fourier transform (IR-FC) was performed on the instrument Perkin Elmer 2000. Filmed four scans with a resolution of 4 cm-1.

The baseline were approximately 980 cm-1up to 840 cm-1. The height of the peaks was determined around the eye is about 888 cm -1for vinylidene, about 910 cm-1for vinyl and approximately 965 cm-1for TRANS-vinylene. The number of double bonds/1000 carbon atoms was calculated by the formula:

Vinyliden/1000 carbon atoms=(14×A)/(18,24×L×D)

Vinyl/1000 carbon atoms=(14×A)/(13,13×L×D)

TRANS-vinile/1000 carbon atoms=(14×A)/(15,14×L×D)

where

A: the absorption peak (peak height)

L: film thickness in mm

D: density of material (g/cm3)

C) determining the content of the vinyl, resulting from polyunsaturated compounds

The number of vinyl groups originating from the polyunsaturated co monomer, per 1000 carbon atoms was determined and calculated as follows,

The investigated polymer and polymer for comparison was obtained in the same reactor, essentially using the same conditions, i.e. the same maximum temperature, pressure and performance, with the only difference consisting in the fact that the examined polymer was added polyunsaturated comonomer and not added to the polymer for comparison. The total number of vinyl groups of each polymer was determined by infrared spectroscopy with Fourier transform, as described above. Then suggested that the main content of the vinyl groups, i.e. groups formed during the process and agent transfer chain of the vinyl groups (if present)is the same on the I polymer for comparison and for issleduemogo polymer, except that for the studied polymer in the reactor was added polyunsaturated comonomer. This basic content is then subtracted from the measured amount of the vinyl groups of the investigated polymer, thereby obtaining the number of vinyl groups/1000 carbon atoms, resulting from polyunsaturated co monomer.

g) Density

The density of the polymer was measured according to ISO 1183/D.

2. Brewed and studied composition

a) Obtaining additives for the stabilization of the electric strength

Unless otherwise stated, all reagents are commercially

available or can be obtained using methods well known

from the literature.

Example 1: the pair-Anisyl Synthesis of para-anisyl

to 25.3 g of steam-Arizona used immediately upon receipt from Sigma Aldrich, was dissolved in 184 ml of dimethyl sulfoxide, and the mixture was intensively stirred for 15 min at room temperature. 50 ml of 48% Hydrobromic acid was added dropwise over 8 minutes, the Solution was heated to 50°C. after four hours the temperature was increased to 90°C and left overnight. The yellow solid was formed after adding NVG, and additional amounts were formed during the night. The product was recrystallized and washed in ethanol. Got to 22.7 g of yellow needle crystals (molar vychod,3%). Purity was 99.6% according to gas chromatography.

m(r)M (g/mol)n (mol)V(ml)
para-Anisoin25,30272,300,093
Dimethyl sulfoxide (DMSO)184
NVG (48%)80,910,3050
pair-Anisyl22,7270,280,084

Example 2: 4,4'-dihydroxybenzyl

Synthesis of 4,4'-dihydroxybenzyl

12 g Anisia was dissolved in 120 ml of acetic acid and 240 ml of 48% Hydrobromic acid. The mixture was intensively stirred and boiled under reflux for 4 hours. The temperature was then reduced to 90°C and left overnight. The resulting solution was poured into the Le and the precipitate was collected by filtration and washed with water. After drying, got 10,43 g of product (yield: 75,0 mol%)having a purity of 76.8%. The purity was measured using gas chromatography.

m(r)M (g/mol)n (mol)V(ml)
pair-Anisyl12270,280,044
NVG (48%)80,911,42240
Acetic acid (Us)60,052,10120
4,4'-Dihydroxybenzyl (76,8%)10,43242,230,033

Example 3: 4,4'-di(dodecyloxy)benzyl

Synthesis of 4,4'-deterimental

3 g of 4,4'-dihydroxybenzyl (76,8%) was mixed with of 6.78 g of n-bromododecane used immediately upon receipt from Sigma Aldrich, was added 2 g of Tetra-n-butylammonium bromide and 3.98 g of potassium carbonate. Added 90 ml of di is malformed, and the mixture was stirred in a round bottom flask at 90°C during the night. Found the change in colour with a yellow/orange to red and then to yellow. Added 100 ml of water, and the product was then extracted first with simple ether and then was perestrelivali with ethyl acetate and washed three times with water. The remaining solution was dried over MgSO4, was filtered and was evaporated in a rotary evaporator. Spent separation on a column of silica with a 50/50 (vol./about.) dichloromethane/n-hexane, and the product was isolated together with the remaining bromoalkane. The product was recrystallized from ethanol, filtered and dried to obtain 5,12 g of 4, 4'-deterimental (yield: 93 mol%).

m(r)M (g/mol)n (mol)V (ml)
4, 4'-dihydroxybenzyl (76,8%)3242,230,00951
Tetra-n-butylammonium bromide (TBAB)2322,370,0062
Dimethylformamide (DMF) 73,091,1690
To2CO33,98138,210,0288
p-Bromododecaneof 6.78249,230,0272
4,4'-Geodecisions5,12578,860,00884

1H NMR (nuclear magnetic resonance) [Chloroform-D, δ]: 0,87(t, 6N), 1,25 (m, 36N), to 1.79 (m, 4H), 4,01 (t, 4H), 6,94 (d, 4H), 7,92 (d, 4H) Example 4: 4,4'-di(undec-10-enyloxy)benzyl Synthesis of 4,4'-di-11-underenrollment

1.5 g of 4,4'-dihydroxybenzyl (76,8%) was mixed with 1.0 g of Tetra-n-butylammonium bromide, 2,88 g of potassium carbonate and 3.2 g of 11-bromo-1-undecene used immediately upon receipt from Sigma Aldrich, 45 ml of dimethylformamide. The mixture was heated to 120°C in an atmosphere of N2 and instensive stirring and left overnight. Added 50 ml of 2M HCL, and the solution was extracted with 50 ml of simple ether and twice was perestrelivali 20 ml simple ether. The ether phases were combined and three times washed with 2M HCI. The resulting substance was purified on column d is silicon oxide with eluent dichloromethane/n-hexane with regard to 1/10 (vol./vol.). The substance was evaporated and then recrystallized from atola. After drying, the total number of product 1,82 g (yield: 70,8 mol%).

m (r)M (r/mol)n (mol)V(ml)
4, 4'-dihydroxybenzyl (76,8%)1,5242,230,0047
Tetra-n-butylammonium bromide (TBAB)1322,370,0031
Dimethylformamide (DMF)73,090,58145
To2CO32,88138,210,0208
11-bromo-1-undecen3,2233,190,01372,976
4,4'-di-11-undecyloxy1,82 546,780,00333

1H NMR [Chloroform-D, δ]: 1,29 (m, 24N) to 1.79 (m, 4H), 2,02 (m, 4H), 4,01 (t, 4H), 5,00 (m, 4H), and 5.8 (m, 2H) 6,94 (d, 4H), to 7.93 (d, 4H)

Example 5: m,M,M1G-atractiveness-4,4'-diamine

m (r)M (r/mol)n (mol)V(ml)
4,4'-dibromobenzyl2,78368,020,00755
The potassium hydroxide (KOH)1,3556,1080,024
cetyl-ammonium bromide0,0456364,460,000125
bis(tri-tert-butylphosphine)0,1015100,000197

palladium (0)
Toluene15
Deionized water4,5
Dioctylamine7,26241,350,03015,8
N,N,N',N'-atractiveness-4,4'-diamine (product)0,75689,110,00109

1H NMR [Chloroform-D, δ]: 0,86 (t, N), of 1.28 (m, N), of 1.57 (m, 8H), and 3.31 (t, 8H), to 6.57 (d, 4H), of 7.82 (d, 4H).

cetyl-ammonium bromide and 0.10 g of bis(tri-tert-butylphosphine)palladium(O) in dvuhholos flask, which is then equipped with a condenser and closed by a rubber membrane. After three cycles of vacuum/purge N2the mixture was left under nitrogen by adding 15 ml of toluene and 4.5 ml of deionized water, each of which has degirolami nitrogen. Under stirring was added dropwise 5.8 ml of dioctylamine, after which the solution was boiled under reflux for 20 hours, the Reaction mixture was then extinguished deionize the trated water, thrice was extracted with dichloromethane, washed twice with brine (saturated aqueous NaCl) and dried over magnesium sulfate. The mixture was applied on a column of silica using dichloromethane with 5% ethyl acetate as solvent. Received 0.75 g of pure product in the form of a viscous yellow oil. Reached out to 14.4 mol.%.

b) Preparation and study of compositions

Prepared several compositions containing additives for the stabilization of the electric strength for receiving insulating layers, and explored together with the polymer for comparison, not containing additives for the stabilization of the electric strength in accordance with the following methods:

Materials and testing the installation to test the electrical Taringa.

In each test for common definitions and examples of the application structure tests for polymer comparison, i.e. a polymer that does not contain substances additives for the stabilization of the electric strength subject to study, and for the studied compositions, i.e. polymer comparing containing substances additives for the stabilization of the electric strength was the same.

Commercially available cross-link polyethylene low density (LDPE) with the trade name Supercure™ LS4201S supplied by Borealis, Sweden received put the m polymerization under high pressure and characterized by density 0,922 g/cm 3(ISO 1872-2/IS-2), P2(ISO 1133, load of 2.16 kg at 190°C.), equal to 2 g/10 min, was used as a polymer for the preparation of the investigated compositions, as well as the studied polymer for comparison.

The polymer for comparison were in the form of granules containing Dicumyl peroxide as cross-linking agent.

Preparation of samples for research electric Taringa

The impregnation

Polymer beads of comparison for the study of electrical tryinga were crushed to fine powder in a machine for grinding Retsch cell sieves 500 micrometers. To obtain compositions according to the invention and obtain compositions for comparison of the obtained powder was soaked corresponding to the investigated additive for stabilizing the electric strength in solution in dichloromethane for one hour, stirring every 15 minutes. Later in the rotary evaporator in a vacuum furnace solvent was removed to obtain a dry powder with homogeneous distributed additive for stabilizing the electric strength.

As additives for the stabilization of the electric strength used the following compounds in the indicated amounts based on the total weight of the composition:

Example 3: 4,4'-di(dodecyloxy)benzyl

Example 4: 4,4'-di(undec-10-enyloxy)benzyl

Example 5: N,N,N,N-tetrac ylbenzyl-4,4'-diamine

Preparation of the studied objects

Impregnated powder is then melted in a plate thickness of 6 mm in accordance with the following procedure melting and cross-stitching. The cycle of melting and cross-stitching plates began with a 2 kN for 3 minutes and ranged from 2 kN to 200 kN for 18 minutes with an increase download speed 11 kN/min and then maintained at 200 kN for the remaining cycle time of melting and cross-stitching. During the melting cycle the temperature was maintained at 130°C at the beginning of the cycle and kept at this temperature during the first six minutes, after which the temperature was increased to 180°C for 15 minutes at the rate of increase of temperature of 3.3°C/min and maintained at 180°C for 15 minutes to complete cross stitch plate and then cooled to room temperature over a period of approximately 30 minutes. Pressed plates were degirolami at a pressure of 1 ATM. at 90°C for 4 days. Then the samples were cut into fragments of 25.5 mm×21 mm×6 mm (+/- 0.5 mm). For forming the electric field required for electrical Taringa, used a sharp tip with a radius of 3 μm and a blunt needle with a tip radius of 5 mm Before using the needle was checked and washed with isopropanol. The needle was then inserted into the PLA is Tinku from opposite sides of each of the surfaces 21 mm×6 mm, with clamp to ensure alignment of the needles, as described in "ASTM D3756-97(2004) Standard Test Method for Evaluation of Resistance to Electrical Breakdown by Treeing in Solid Dielectric Materials Using Diverging Fields," Series E., Ed., ed: ASTM International, 2004. Sharp needle had a radius of 3 μm, and a blunt needle had a radius of 0.5 mm Before the introduction of the needle plate retainer plates were placed in an oven at 120°C for 90 minutes, after which the needle was slowly loaded up until they were at a distance of 3.5 mm Samples left in an oven at 120°C for another 30 minutes, and then oven off and leave samples so that they reach the room temperature inside the furnace for 10 hours the Samples were then kept at constant conditions of 23°C and 50% RH (relative humidity) before placing them in the test cell. The study of electrical tryinga also carried out at 23°C and 50% RH. in)

Results

1. The study of electrical Taringa

The electric field at which the insulation material begins to show electric trying, also called the initiation of electrical Taringa, evaluate using the conventional approach with two needles. The configuration of the needle described in detail in A. .Ashcraft, et al., "Labarotory Studies of Treeing in Solid Dielectrics and Voltage Stabilization of Polyethylene," Montreal, Canada, 1978, pp.213-218 and ASTM D3756-97(2004) Standard Test Method for Evaluation of Resistance to Electrical Breakdown by Treeing in Solid Dielectric Materials Using Diverging Fields," Series E., Ed., ed: ASTM International, 2004. Instead of applying a constant voltage AC is spent voltage was increased at a rate of 10 In/min, starting at 8 kV and with the highest level of 22 kV. The electrode system was associated with a partial discharge detector that disables the high voltage detection bits. The samples were then cut into thin layers and examined under a microscope to determine the responsible whether electric trying for the formation of partial discharges in which equipment is disabled. In the case of localization of trying the sample was considered as subjected to breakdown, if trying not found, then the sample was considered as overlapping and he was excluded from statistical evaluation.

2. Analysis of the results

Voltage initiation of trying for the material was determined by applying a two-parameter Weibull statistics in accordance with IEC "Guide for the Statistical Analysis of Electrical Insulation Breakdown Data, Vol.IEC 62539:2007(E)ed. Geneva: The International Electrotechnical Commission (IEC), 2007 in respect of registered breakdowns. In accordance with statistics, Weibull received the scale parameter using commercially available software WinSmith Weibull 4.0 Fulton Findings and represented in the form of initiation voltage electrical Taringa.

To compare the effectiveness of various additives used factor MVS (molar region of stability), based on a molar basis (A. .Ashcraft, et al., "Labarotory Studies of Treeing in Solid Dielectrics and Voltage Stabilization of Polyethylene," Montreal, Canada, 1978 pp.213-218). MVS is defined as the difference between the material used for comparison, with and without stabilizer, divided by the molar amount of added stabilizer.

Results
nSusp.αβTIV [kV]ΔkVMVS [kW kg/mol]
To compare20312,95,112,9
Example 310521,72,821,78,71442
Example 410629,82,729,816,92639
When is EP 5 10418,22,918,25,31036

n: number of tested samples,

susp. The number of suspended samples,

the α and β parameter B scale and form receive, respectively, according to the statistics Weibull,

TIV voltage initialization trying,

ΔkV the difference in voltage between the sample for comparison and a test specimen

MVS Molar region of stability.

From the above table, we can see that the claimed examples 3-5 demonstrate significantly increased the voltage initialization triing compared to the material used for comparison.

1. Polyolefin composition for receiving layer of the cable containing:
A. the polyolefin (A),
B. benzyl derivative (B)containing a structural unit of the formula (I):

where
one or more than one carbon atom in the phenyl ring to which is attached the residues R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 may also be a heteroatom, such as N, in this case, the corresponding residues R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 is absent;
R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 independently of one another are hydrogen or uglevodorodno the th group, which may contain heteroatoms;
or at least two of the above R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 together with the ring atoms of the ring system of the formula (I), to which they are attached, form an additional aromatic or non-aromatic ring condensed with a ring system of formula (I), and where the ring system of the formula (I) with the specified at least one more condensed ring may also contain from one to eight substituents R1'-R8", each of which is independently selected from the specified the same groups as R1-R10; and
n=from 2 to 9,
provided that
(i) at least one of the R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10, or, if there is at least one of the R1'-R8' represents a hydrocarbon group which may contain one or more than one heteroatom.

2. Polyolefin composition according to claim 1, where the specified n is from 2 to 6.

3. Polyolefin composition according to claim 1 or 2 where the specified hydrocarbon group according to condition (i) contains a heteroatom selected from the group consisting of Si, N, P, O and S.

4. Polyolefin composition according to claim 3, where the heteroatom represents N and the specified hydrocarbon group provided that (i) contains a tert-amino group.

5. Polyolefin composition according to claim 1, where at least one of the R1, R2, R3, R4, R5, R6, R7, R8, R9 and and R10, or, if there is at least one of the R1'-R8' represents a hydrocarbon group according to condition (i) and is selected from-N(R11)(R12) and-Ar-N(R11)(R12), where R11 and R12 independently represent a hydrocarbon group that may contain heteroatoms, and Ar represents an aryl group which may contain heteroatoms.

6. Polyolefin composition according to claim 1, where specified, at least one of the R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10, or, if present, at least one of the R1'-R8' represents a hydrocarbon group according to condition (i) and is selected from-O(R13), and-Ar-O(R13)where R13 represents H or a hydrocarbon group which may contain heteroatoms, and Ar represents an aryl group which may contain heteroatoms.

7. Polyolefin composition under item 5 or 6, where R11, R12 and R13 independently represent aryl or alkyl group.

8. Polyolefin composition under item 5 or 6, where-N(R11)(R12), or-O(R13) is in the para-position relative to the carbonyl functional group in the compound of formula (I).

9. The polyolefin composition of claim 8, where R8 and R3 is substituted specified-N(R11)(R12), or-O(R13).

10. Polyolefin composition under item 5 or 6, where R11, R12 and R13 independently represent an alkyl group, which may contain or not contain funkcionalno the group at the end, opposite the corresponding ring atom.

11. Polyolefin composition under item 5 or 6, where R11, R12 and R13 independently contain from 1 to 50 carbon atoms.

12. Polyolefin composition according to claim 11, where R11, R12 and R13 independently contain from 6 to 18 carbon atoms.

13. Polyolefin composition according to item 12, where R11, R12 and R13 independently contain from 6 to 12 carbon atoms.

14. Uterine mixture to obtain a layer of a cable, comprising:
(1) the polymer matrix in an amount of 50 wt.% or more, and
(2) benzyl derivative (B)containing a structural unit of the following formula (I):

where
one or more than one carbon atom in the phenyl rings, which are attached to the residues R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 may also be a heteroatom, such as N, in this case, the remainder of R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 is absent;
R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 independently of one another are hydrogen or hydrocarbon group which may contain heteroatoms;
or at least two of the above R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 together with the ring atoms of the ring system of the formula (I), to which they are attached, form an additional aromatic or non-aromatic ring condensed with a ring system of formula (I), and where the ring system of the formula (I) specified, at measures which, one more condensed ring may also contain from one to eight substituents, R1' to R8', each of which is independently selected from these same groups as R1-R10; and
n=from 2 to 9,
provided that
(i) at least one of the R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10, or, if there is at least one of the R1'-R8' represents a hydrocarbon group which may contain one or more than one heteroatom.

15. Uterine mixture 14, where the benzyl derivative (C) is determined according to any of claim 2 to 13.

16. A cable comprising a layer made from a polyolefin composition according to any one of claims 1 to 13.

17. The cable according to clause 16, where a cable is a cable medium, high or extra-high voltage containing an inner semi-conducting layer, an insulating layer and an outer semi-conducting layer.

18. The cable 17, where at least the insulating layer is made of a polyolefin composition according to any one of claims 1 to 13.

19. The application of the polyolefin composition according to any one of claims 1 to 13 for receiving a layer of the cable.

20. The use of masterbatches in 14 or 15 for receiving a layer of the cable.

21. The use of benzyl derivative (B) as an additive to stabilize the electric strength of the polyolefin composition, where the benzyl derivative (b) contains a structural single the HQ of the formula (I):

where
one or more than one carbon atom in the phenyl rings, which(th) attached residues R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 may(ut) represent a heteroatom(s), so(s), as N, in this case, the corresponding residues R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 is absent;
R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 independently of one another are hydrogen or hydrocarbon group which may contain heteroatoms;
or at least two of the above R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10 together with the ring atoms of the ring system of the formula (I), according to which they are attached, form an additional aromatic or non-aromatic ring condensed with a ring system of formula (I), and where the ring system of the formula (I) with the specified at least one more condensed ring may also contain from one to eight substituents, R1' to R8', each of which is independently chosen of these the same groups as R1-R10; and
n=from 2 to 9,
provided that
(i) at least one of the R1, R2, R3, R4, R5, R6, R7, R8, R9 or R10, or, if there is at least one of the R1'-R8' represents a hydrocarbon group which may contain one or more than one heteroatom.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: electrically insulating composition contains suspended polyvinyl chloride, an ester plasticiser, a lead stabiliser, diphenylol propane, chalk, stearic acid, calcium stearate, epoxidated soya bean oil, magnesium hydroxide, ammonium polyphosphate, chlorinated paraffins, antimony trioxide, zinc oxide, boric acid and organoclay.

EFFECT: low level of smoke emission in burning and glowing conditions while maintaining the degree of incombustibility.

2 cl, 1 tbl

FIELD: electricity.

SUBSTANCE: electric insulating composition includes suspension polyvinyl chloride, ester plasticiser, diphenyl propane, lead stabiliser, stearic acid, lubricating material, epoxidated soya oil, chlorinated paraffin, magnesium hydroxide, ammonia polyphosphate and organic clay.

EFFECT: invention makes it possible to produce a composition with lower combustibility, low release of smoke and hydrogen chloride during combustion, and to increase value of physical and mechanical characteristics.

1 tbl, 6 ex

FIELD: electricity.

SUBSTANCE: electroconductive peroxide cross-linkable composition comprises, wt %: polyolefin 49-62, benzopropionic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxy-2-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl] hydrazide -0.05-0.20, tetra-bis-methylene-(3-(3,5-di-tret-butyl-4-hydroxyphenyl) propionate)-0.05-0.20, organic peroxide-0.2-1.9, electroconductive technical carbon with specific volume resistance p=10±6 Ohm*cm - 29-34, technical carbon with specific volume resistance p=5±3 Ohm*cm - 2.5-5, 4,4'-thiabis(6-tret-butyl-m-cresol) - 0.05-0.25, zinc stearate - 0.15-1.0, polyethylene wax - 3-9. The composition of the specified compound is not exposed to substantial thermal-oxidative ageing and premature cross-linking during superimposition, and items from it have smooth surface.

EFFECT: improved physical and mechanical properties of cable products made with application of the proposed composition, and its manufacturability and stability.

2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to electrical engineering, specifically to cable engineering and polymer compositions based on plasticised polyvinyl chloride (PVC) with low inflammability, release of smoke and hydrogen chloride during combustion, intended for insulating inner and outer sheaths of cables. The electrically insulating composition contains suspended polyvinyl chloride, an ester plasticiser - dioctyl phthalate, tricresyl phosphate, chalk, soot, a stabiliser - melanine, antipyrenes - magnesium hydroxide and ammonium polyphosphate, smoke absorber - chlorinated paraffins, lubricant agent - calcium stearate, antioxidant - diphenylol propane and filler - organoclay, which is a product of modifying montmorillonite from the Gerpegezh deposit of the Kabardino-Balkaria Republic with cation-exchange capacity of 95 mg-eq/100 g clay with urea, in amount of 10% of the mass of montmorillonite.

EFFECT: obtaining a composition characterised by high non-flammability and low release of smoke during combustion.

2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to cable engineering and specifically to polymer compositions based on plasticised polyvinyl chloride (PVC) with low inflammability and release of smoke in combustion and smouldering conditions and release of hydrogen chloride during combustion, meant for insulating inner and outer sheaths of wires and cables used in high fire hazard conditions. The electrically insulating composition contains suspension polyvinyl chloride, an ester plasticiser, a lead stabiliser, calcium carbonate, a trihydrate of aluminium oxide or magnesium hydroxide, antimony trioxide, calcium stearate, zinc oxide, zinc borate, a bromine-containing fire retardant, boric acid and diphenylol propane.

EFFECT: invention improves fire safety of wires and cables, reduces smoke-formation during smouldering or combustion and provides low inflammability.

1 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a heterophase polypropylene resin, a method of producing such a polypropylene resin and use thereof in making articles, particularly as material for making insulation and semiconductor layers of power cables. The heterophase polypropylene resin contains a matrix phase of a propylene radom copolymer and a rubber phase of an ethylene-propylene copolymer dispersed in the matrix phase. The heterophase polypropylene resin is characterised by melt flow rate (2.16 kg, 230°C) from 1.0 to 100 g/10 min, determined according to ISO 1133, and a fraction which is soluble in p-xylene at 25°C (XCS fraction), which is present in the resin in amount of 28 to 50 wt % and has molecular weight distribution (Mw/Mn) from 1.0 to 4.0.

EFFECT: heterophase polypropylene resin has high softness, improved low-temperature impact characteristics and a high melting point.

14 cl, 3 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: composition contains the following in pts.wt: suspended polyvinyl chloride 100, ester plasticiser 40-60, tribasic lead sulphate 3-7, calcium stearate 1-3, calcium carbonate 5-7, trihydrate of aluminium oxide and/or magnesium hydroxide 20-80, antimony trioxide 2-9, zinc oxide 1-5, ionol 0.1-0.5, zinc borate 0.5-6, diphenylol propane 0.1-0.5 percalite F 100 - 0-5 metal-containing lubricant 0.5-10, wherein the metal-containing lubricant is obtained by reacting oleic or stearic acid with glycerol in molar ratio 1:1 in the presence of 0.5-2.0 wt % of the total reaction mass of zinc oxide or magnesium oxide or two-component mixture thereof, with weight ratio thereof of 0.25-1.0:0.25-1.0 at 130-160°C and holding for 4-5 hours. High melt fluidity of the disclosed composition makes easier its processing in high-speed extruders.

EFFECT: low coefficient of smoke formation, high degree of incombustibility, processability of the composition and improved outer appearance of a bundle of the cable plastic compound.

1 tbl, 1 ex

FIELD: electrical engineering.

SUBSTANCE: method for production of insulated HV direct current (DC) eclectic cable or HV direct current (DC) eclectic cable or HV direct current (DC) lead or HV junction involves the stages of a polymer-based insulation system production (21), the system including a stirred polymer composition (12). Further thermal treatment (25) of the polymer-based insulation system is performed until the outside surface of the polymer-based insulation system is coated (24) with a coating impermeable for the substance present in the polymer-based insulation system as evenly distributed. Thus the concentration of the substance in the polymer-based insulation system is levelled.

EFFECT: manufacture time reduction, electric strength enhancement and maintenance simplification.

19 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to cable engineering and can be used for insulation and sheathing of cables and wires used in high fire hazard conditions. The electrically insulating composition contains a polyvinyl chloride composition I 40-13 A and a fire-retarding agent in form of montmorillonite which is modified with 5-15% urea or melamine, and magnesium hydroxide.

EFFECT: high fire-resistance of the composition and low smoke emission in the high fire hazard zone.

1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: electrically insulating composition contains I 40-13A PVC compound, an antipyrene in form of ammonium polyphosphate and organoclay which is a product of modifying montmorillonite with cation-exchange capacity of 95 mg-eq/100 g clay with melamine in amount of 10% of the mass of montmorillonite.

EFFECT: reduced inflammability, low smoke toxicity, low cost of plasticised polyvinyl chloride.

2 dwg, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: by increasing resistance to inflammation in combustion conditions, the electrically insulating material, which is obtained from additive vulcanisation silicone rubber, simultaneously contains vinyl and hydride-containing siloxanes, a cyano-containing organophosphorus compound in amount of 40-70 pts.wt and/or modified aluminium hydroxide in amount of 10-150 pts.wt per 100 pts.wt polyorganosiloxane, filler materials and polymers with block trimethyl-containing siloxane links that are cross-linked under the action of a platinum catalyst, wherein the latter is added to the rubber mixture before use thereof. The siloxane rubber can further contain powdered quartz in amount of 10-40 pts.wt per 100 pts.wt polyorganosiloxane.

EFFECT: high resistance of the electrically insulating material to inflammation in combustion conditions.

3 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: there is disclosed insulating coating composition, containing bitumen in amount 90-100 wt fractions, fluorocarbon polymer 32 LN in amount 10-15 wt fractions, butyl acetate in amount 40-45 wt fractions, acetone in amount 40-45 wt fractions and mica in amount 2-3 wt fractions.

EFFECT: improved insulating properties, mechanical strength and chemical stability.

1 tbl, 1 ex

FIELD: electricity.

SUBSTANCE: invention is attributed to the field of electric engineering specifically to epoxide thin filling compounds used for electric insulating and reinforcing by means of embedding of high-voltage power supply units, transformers, electric circuitry, uncased and cased electric couplers, for sealing and protecting elements of radio-electronic devices against moisture and mechanical impacts. Composition for filling compound with moderate initial viscosity contains 30-36 wt-p. of epoxide diane resin, 12-20 wt-p. of threeglycid polyoxypropylene triol ether, 10-12 wt-p. of monoglycid n-butanol ether, 18-22 mass-p. of low-polymeric polyamid resin and 7-10 wt-p. of aliphatic amine.

EFFECT: creation of electric insulating filling compound composition keeping resiliency not less than for an hour, having high specific volume, high value of surface electric resistance and increased elasticity.

1 tbl

Insulating material // 2284593

FIELD: electrical engineering.

SUBSTANCE: proposed insulating material that can be effectively used to insulate conductors for various industries, including radio engineering, cable industry, microelectronics, and the like, has multilayer structure of N thin-film layers, where N > 1; all layers are made of separate piled films produced from same material and by same method, having actually equal thickness d < 25 μm.

EFFECT: facilitated manufacture, reduced cost of materials used, enhanced electric and mechanical strength.

1 cl, 1 dwg, 2 tbl

FIELD: marking materials.

SUBSTANCE: invention relates to pigmentation and compositions for use in laser marking, in particular UV absorbing pigment at least partly covered with synergist having general formula [Rm(SiOn)]pR'q wherein m=1-3, n=1-3, p is a number equal to at least 1, q=0-3, and at least one of R or R' represents substituent. When pyrolized, pigment forms black material appropriate to form label. Such pigments are suitable for fluoropolymers serving to insulate wire conductors and cables.

EFFECT: expanded marking possibilities.

20 cl, 6 tbl, 38 ex

FIELD: electronic engineering; gas panel manufacture.

SUBSTANCE: protective coating that can be used for manufacturing contact members of gas-panel strip conductors is formed on both sides of polyamide and applied by stenciling method using for the purpose dielectric composition resistant to 20-30% alkali solutions at temperature of 65 - 85oC that incorporates in its composition ethyl cellulose in the amount of maximum 9 parts by weight and organic solvent in the amount of minimum 91 parts by weight with boiling temperature of ≥ 190oC, minimal amount of ethyl cellulose and maximal amount of organic solvent being, respectively, 7.5 and 92.5 parts by weight.

EFFECT: improved rheological and protective properties of coating using proposed composition.

1 cl, 1 ex

The invention relates to the field of electrical insulating equipment, in particular the silicone composition used in the electrical industry for the production of insulating materials and for impregnation of windings of electrical machines and apparatus

The invention relates to the field of electrical engineering, in particular to compositions based on ethylene-propylene rubber, used as maguilera placeholder in electric cables and wires

The invention relates to the field of electrical engineering, in particular to compositions for the manufacture of coatings for electrical steels for magnetic circuits of electrical machines and apparatus

The invention relates to the production of insulating coatings on electrical steel used in the magnetic circuits of electrical machines, apparatus and instruments

FIELD: chemistry.

SUBSTANCE: invention relates to polymerisation of olefins. Described is a method of polymerising at least one olefin monomer in more than one polymerisation zone of one or more polymerisation reactors using a highly active catalyst, which is fed into the front end of the reactor to form solid polymer particles. The method is carried out in the apparatus.

EFFECT: wider molecular weight distribution of the obtained polymer.

5 cl, 5 dwg, 2 tbl

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