CN102682905A - Medium or high voltage electric cable - Google Patents
Medium or high voltage electric cable Download PDFInfo
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- CN102682905A CN102682905A CN2012101126559A CN201210112655A CN102682905A CN 102682905 A CN102682905 A CN 102682905A CN 2012101126559 A CN2012101126559 A CN 2012101126559A CN 201210112655 A CN201210112655 A CN 201210112655A CN 102682905 A CN102682905 A CN 102682905A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B9/00—Power cables
- H01B9/02—Power cables with screens or conductive layers, e.g. for avoiding large potential gradients
- H01B9/027—Power cables with screens or conductive layers, e.g. for avoiding large potential gradients composed of semi-conducting layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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Abstract
The present invention relates to an electric cable (1), comprising an electric conductor (2), a first semiconducting layer (3) surrounding the electric conductor (2), a second electrically insulating layer (4) surrounding the first semiconducting layer (3), and a third semiconducting layer (5) surrounding the second electrically insulating layer (4). At least one of the three layers (3, 4, 5) is a crosslinked layer obtained from a crosslinkable composition including at least one kind of polyolefin and organic peroxide acting as a crosslinking agent. The composition also includes a crosslinking coagent having at least two unsaturated bonds, and one unsaturated bond therein is a vinyl functional group.
Description
Technical field
The present invention relates to a kind of cable.This cable generally is applied to middle pressure (particularly from 6 to 45-60 kilovolts) or high pressure (particularly greater than 60 kilovolts, can up to 800 kilovolts) power cable field, but is not only to be applied to this, and no matter is that the ac cable or the situation of direct current cables are all set up.
Background technology
The medium-pressure or high pressure power cable generally comprises: center electrical conductor and, the semiconductor internal layer of also coaxial this electric conductor of parcel, electric insulation intermediate layer and semiconductor are outer successively, these three layers know by one of skill in the art technological crosslinked.
Usually, these three cross-linked layers are by the composition based on polyethylene polymer matrix, and for example dicumyl peroxide or tert-butyl peroxide isopropylbenzene (tert butyl cumyl peroxide) are resulting to mix organic peroxide.During crosslinked said composition, this type peroxide breakdown also generates crosslinked accessory substance, mainly is for example methane, acetophenone, cumyl alcohol, acetone, uncle-butanols, AMS and/or water.Above-mentioned last two accessory substances are to be generated by the dehydration of cumyl alcohol.
If the methane that in cross-linking step, generates is not removed, just can not ignore the danger relevant with inflammability with the explosion hazard of methane from cross-linked layer.In case this cable is brought into use, this gas also may cause damage.When the semiconductor skin is wrapped up by metal protection layer, normally this situation in the structure of medium and high pressure cable, said gas can only be along joint and the terminals of this cable longitudinal diffusion up to electric device (electric power accessory just).Therefore methane possibly accumulate and produce the pressure to the electric power accessory, and this possibly cause electrical breakdown.Though be present in the method that restriction methane exists in the cable, for example the heat treatment cable spreads out from cable to quicken methane, and when insulating layer thickness, these methods are consuming time and expensive.
Document US 5 252 676 has been introduced a kind of three-layer insulated layer that is used for power cable.This three-layer insulated layer is to be obtained by following composition, and said composition comprises ethylene copolymer, as the organic peroxide of crosslinking agent with such as the additive of this type of isopropenylbenzene or derivatives thereof.In order to reduce the gas flow that during crosslinking agent decomposes, discharges, said document suggestion reduces the consumption of crosslinking agent.
Yet the cross-linkable composition that uses in the said document provides after making composition crosslinked in the gratifying thermo-mechanical property, aspect the amount that reduces crosslinked accessory substance, is not optimized.
Summary of the invention
The objective of the invention is through providing a kind of medium-pressure or high pressure cable of cross-linked layer that comprises to overcome the defective of prior art; In said cross-linked layer preparation, significantly reduced the for example existence of methane of crosslinked accessory substance; And provide optimal heat mechanical characteristic simultaneously; For example thermal creep property, this is the appropriate crosslinked characteristic of said layer.
A theme of the present invention is a kind of cable; The 3rd semiconductor layer that it comprises electric conductor, wraps up first semiconductor layer of this electric conductor, wraps up second electric insulation layer of this ground floor and wrap up this second layer; In above-mentioned three layers at least one deck be the cross-linked layer that obtains by cross-linkable composition; Said cross-linkable composition comprises at least a polyolefin and as the organic peroxide of crosslinking agent; It is characterized in that: said composition also comprises the crosslinking coagent that contains at least two unsaturated bonds, and a unsaturated bond in these two unsaturated bonds is a vinyl-functional, and said vinyl-functional is CH preferably
2The olefmic functionality of=CH-type.
Be different from said crosslinking agent, crosslinking coagent of the present invention is multifunctional type, because it contains at least two unsaturated bonds.
Said at least two unsaturated bonds more specifically are the reactive functional groups of carbon-to-carbon double bond type, and it at first can be grafted on the said polyolefin, secondly can participate in said polyolefinic crosslinked (formation of the three-dimensional network of said cross-linked polyolefin just).
Said crosslinking coagent can advantageously significantly reduce the ratio that is used in the organic peroxide in the said cross-linkable composition; Thereby reduce the amount of the methane that the crosslinked accessory substance be derived from said peroxide derives; Keep good for example thermal creep property of thermo-mechanical property simultaneously, and gratifying crosslinking rate.According to standard NF EN 60811-2-1, be no more than 100% through the maximum heat percentage elongation under stress, preferably be no more than 80%, and 60%-80% more preferably, can reflect the thermo-mechanical property of cross-linked layer of the present invention easily.
Preferably, use the sufficiently high auxiliary agent of boiling point, so during the step of accomplishing said cross-linkable composition, particularly through during the step of extruding the said cross-linkable composition of completion, it can not evaporate.
For example, said crosslinking coagent can be selected from 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,3-dimethyl-1; 3-butadiene, 2-methyl isophthalic acid, 4-pentadiene, 3-methyl isophthalic acid, 3-pentadiene, 4-methyl isophthalic acid, 3-pentadiene, 1,6-heptadiene, 2,4-dimethyl-1; 3-pentadiene, 2-methyl isophthalic acid, 5-hexadiene, 4-vinyl-1-cyclohexene, 1,7-octadiene, 2,5-dimethyl-1,5-hexadiene, 2,5-dimethyl-2; 4-hexadiene, 5-vinyl-2-ENB, 1,8-nonadiene, 7-methyl isophthalic acid, 6-octadiene, 1,4,9-triolefin in the last of the ten Heavenly stems, 2,6-dimethyl-2; 4,6-sarohornene, cinene, 7-methyl-3-methylene-1,6-octadiene, 1,9-decadinene, 3,9-divinyl-2,4; 8,10-four oxaspiros [5.5] hendecane, 1,2,4-trivinyl cyclohexane, 1,13-14 carbon diene, 2,3-diphenyl-1; 3-butadiene, trans, anti-form-1,4-diphenyl-1,3-butadiene, 1,15-16 carbon diene, 1,6-diphenyl-1; 3,5-hexatriene, 2,3-dibenzyl-1,3-butadiene and polybutadiene, or its mixture.
In an especially preferred embodiment, at least two unsaturated bonds of said crosslinking coagent are vinyl-functional, particularly CH
2The olefmic functionality of=CH-type.
In this case, said crosslinking coagent can be selected from 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1; 8-nonadiene, 1,4,9-triolefin in the last of the ten Heavenly stems, 1,9-decadinene, 3; 9-divinyl-2,4,8,10-four oxaspiros [5.5] hendecane, 1; 2,4-trivinyl cyclohexane, 1,13-14 carbon diene, 1,15-16 carbon diene.
The concentration of said auxiliary agent is preferably limited to the expressing technique that does not destroy cross-linkable composition according to the invention.For example, said cross-linkable composition can comprise the crosslinking coagent of 3 weight portions at the most, with respect to polymer per 100 parts in the said cross-linkable composition.The preferred auxiliary agent that uses 0.5 to 2 weight portion is with respect to polymer per 100 parts in the said cross-linkable composition.
Organic peroxide of the present invention can be selected from organic peroxide well known to those skilled in the art, no matter it is aliphatic series or aromatics peroxide.
The instance of the aromatics peroxide that can mention comprises dicumyl peroxide and tert-butyl peroxide isopropylbenzene.
Aliphatic peroxide (aliphatic peroxide) can be the aliphatic peroxide that comprises at least one tertiary alkyl.The instance of the aliphatic peroxide that can mention comprises:
-aliphatic peroxycarbonates, for example uncle-amyl peroxy carbonic acid 2-ethylhexyl, tertiary pentyl-peroxidating carbonic acid 2-ethylhexyl, tert-butyl hydroperoxide isobutyl carbonate propyl diester;
The aliphatic peroxide of-two tertiary alkyls, for example 1,1-bis(t-butylperoxy) cyclohexane, 2,5-dimethyl-2; 5-bis(t-butylperoxy)-3-hexin, 2,5-dimethyl-2,5-bis(t-butylperoxy)-3-hexane, two-t-amyl peroxy thing, di-tert-butyl peroxide, cyclic peroxide for example 3; 6,9-triethyl group-3,6; 9-trimethyl-1,4,7-three peroxide nonanes;
-aliphatic peroxidating acetal (peroxyacetal), for example 4,4-bis(t-butylperoxy) valeric acid butyl ester; And
-aliphatic peroxyester, for example peracetic acid tertiary butyl ester, peracetic acid tertiary pentyl ester.
Compare with the aromatics peroxide; The advantage of aliphatic peroxide is during said cross-linkable composition crosslinked, not generate crosslinked accessory substance cumyl alcohol (cumyl alcohol); Thereby can reduce the existence of water in the said cross-linked layer significantly, keep good thermo-mechanical property simultaneously.
In the said aliphatic peroxide of mentioning, preferably use the aliphatic peroxide of two tertiary alkyls.Reason is, this type of peroxide can be during realizing composition, makes between the danger of crosslinking rate and incipient scorch (burnout) or precrosslink to reach good balance.
Preferably, said cross-linkable composition does not comprise any aromatics peroxide, particularly dicumyl peroxide or derivatives thereof for example.
The peroxide method of cross-linkable composition of the present invention is crosslinked, can under heat and pressure effect, carry out, and for example under nitrogen pressure, uses curing tube, and this crosslinking technological is well known to those skilled in the art.
Cross-linkable composition according to the invention can comprise the organic peroxide that is no more than 2.00 weight portions, with respect to the polymer of per 100 weight portions in the said composition; Preferably be no more than the organic peroxide of 1.50 weight portions, with respect to the polymer of per 100 weight portions in the said composition; Preferably be no more than the organic peroxide of 1.25 weight portions, with respect to the polymer of per 100 weight portions in the said composition; And the organic peroxide that especially preferably is no more than 1.10 weight portions, with respect to the polymer of per 100 weight portions in the said composition.
Said term " polyolefin " generally is meant olefin homo or copolymer in essence.It can represent thermoplastic polymer or elastomer especially.
Preferably, said olefin polymer is Alathon or ethylene copolymer.
The polyvinyl instance that can mention comprises: the copolymer (2HEA) of the copolymer (EMA) of copolymer (EBA), ethene and the methyl acrylate of copolymer (EVA), ethene and the butyl acrylate of LLDPE (LLDPE), low density polyethylene (LDPE) (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) (HDPE), ethene and vinyl acetate, ethene and acrylic acid 2-hexyl ethyl ester; The copolymer of ethene and alpha-olefin; For example polyethylene-octene (PEO), polyethylene-butylene (PEB); The copolymer of ethene and propylene (EPR); For example ethylene-propylene-diene terpolymer (EPDM), and their mixture.
The preferred low density polyethylene (LDPE) (LDPE) that uses because it has the characteristic that good being used to realizes rheological characteristic, is particularly realized through extruding, and good thermo-mechanical property and electrical properties.
Said term " low-density " refers to particularly 0.910-0.940g/cm
3Density, and preferred 0.910-0.930g/cm
3Density, according to standard ISO 1183 (under 23 ℃ of temperature).
Generally, said low density polyethylene (LDPE) (LDPE) can obtain through the polymerization process in high pressure tubular reactors or the autoclave reactor.
Said cross-linkable composition can comprise the polyolefin greater than 50.0 weight portions, with respect to the polymer (polymer substrate just) of per 100 weight portions in the said composition; The polyolefin of preferred at least 70 weight portions is with respect to the polymer of per 100 weight portions in the said composition; And the polyolefin of preferred especially at least 90 weight portions, with respect to the polymer of per 100 weight portions in the said composition.
In a kind of particularly advantageous mode, said cross-linkable composition comprises the polymer substrate of only being made up of polyolefin or polyolefin blend.
Cross-linkable composition according to the invention can also comprise, contains the aromatic compounds that at least one armaticity is examined (aromatic nucleus) and can be grafted to the single reaction property functional group on the polyolefin.Preferably, the reactive functional groups of said aromatic compounds is a vinyl-functional.Therefore, compare with said crosslinking coagent, when this aromatic compounds was present in the said cross-linkable composition, it did not participate in polyolefinic crosslinked.
In field of cables, the cross-linked layer that is obtained by this cross-linkable composition has enhancing and durable performance, demonstrates anti-preferably water tree property (resistance to water treeing).More particularly, it relates to anti-electrical breakdown property, especially, and to the elimination ability of the space charge accumulated in the high-tension cable under the direct current particularly.
Said aromatic compounds can be selected from styrene, styrene derivative and its isomers.
The instance of the styrene derivative that can mention comprises the compound with following general formula:
Wherein, X is hydrogen, alkyl or aryl; And R is hydrogen, alkyl or aryl.More particularly, can mention 4-methyl-2,4-diphenyl amylene (pentane) and triphenylethylene.
In scope of the present invention, polycyclic aromatic hydrocarbon (PAH) type styrene derivative also is admissible.More particularly, can mention vinylnaphthalene for example 2-vinyl naphthalene, vinyl anthracene for example 9-vinyl anthracene or 2-vinyl anthracene and vinyl phenanthrene for example the 9-vinyl is luxuriant and rich with fragrance.
These aromatic compounds are grafted on the polyolefin polymers chain, generally be at polyolefinic cross-linking stage in the presence of tertiary alkyl aliphatic peroxide of the present invention, carry out according to free radical addition mechanism well known to those skilled in the art.
Cross-linkable composition of the present invention can also comprise at least a protective agent, for example antioxidant.Antioxidant can protect said composition not receive in the preparation process of cable or the thermal limit that runs in the use of cable.
Said antioxidant preferably is selected from:
-hindered phenolic antioxidant, for example tetramethylene (4-hydroxyl hydrogenation-cinnamic acid 3,5-two-tertiary butyl ester) methane, 3-(3; 5-two-tertiary butyl-4-hydroxy-phenyl) propionic acid stearyl, 2,2 '-sulfo-divinyl two [propionic acid 3-(3,5-two-tert-butyl group-4-hydroxyphenyl) esters], 2; 2 '-thiobis (the 6-tert-butyl group-4-sylvan), 2,2 '-di-2-ethylhexylphosphine oxide (the 6-tert-butyl group-4-sylvan), 1,2-two (3; 5-two-tertiary butyl-4-hydroxy hydrogenation-cinnamoyl) hydrazine, [2; 2 '-oxamido-two (3-(3,5-two-tert-butyl group-4-hydroxyphenyl) propionic acid ethyl esters) and 2,2 '-oxamido-pair-[3-(tert-butyl group-4-hydroxyphenyl) propionic acid ethyl ester];
-thioether; For example 4; Two (octyl group sulfidomethyl) orthoresols of 6-, two [2-methyl-4-{3-is alkylthio group-propiono oxygen base just-(C12 or C14) }-5-tert-butyl-phenyl] sulfide and thiobis [the 2-tert-butyl group-5-methyl-4,1-phenylene] two [3-(dodecane sulfenyl)-propionic ester];
-sulphur type antioxidant, for example 3,3 '-the two stearyl or 3,3 of thio-2 acid '-the two dodecyl esters of thio-2 acid;
-phosphorus type antioxidant, for example phosphite ester or phosphonate ester, for example three (2,4-two-tert-butyl-phenyl) phosphite esters or two (2,4-two-tert-butyl-phenyl) pentaerythritol diphosphites; And
-amine type antioxidant for example gathers 2,2,4-trimethyl-1,2-EEDQ (TMQ), the antioxidant of preferred especially latter type in composition of the present invention.
TMQ can be different rank, that is:
-have " standard " level of low polymerization degree, promptly residual monomer content greater than 1wt% and residual NaCl content 100ppm to greater than 800ppm (per 1,000,000/, in mass);
-have " high polymerization degree " level of high polymerization degree, promptly residual monomer content arrives greater than 800ppm at 100ppm less than 1wt% and residual NaCl content;
-residual NaCl content is less than " low-residual salt content " level of 100ppm.
The selection of the type of stabilizer and content in the said cross-linkable composition, usually with polymer during the mixture preparation and relevant through extruding the maximum temperature that during realization on the cable, will stand, and depend on the longest exposure time under this temperature.
Said cross-linkable composition generally can comprise the antioxidant of 0.1wt% to 2wt%.Preferably, comprise when the antioxidant that is no more than 0.7wt%, particularly antioxidant are TMQ.
Other additive well known to those skilled in the art and/or filler also can add in the cross-linkable composition of the present invention; For example puncture delayer (breakdown retardant), processing aid for example lubricant or wax, bulking agent, coupling agent, ultra-violet stabilizer, non--conductive filler, conductive filler, and/or semiconductor fills.
According to a preferred embodiment, cross-linked layer according to the invention is electric insulation layer (second layer just).When it was electric insulation layer, said cross-linkable composition did not comprise any (on the electricity) conductive filler and/or does not comprise any semiconductor fills.
More particularly, at least two is cross-linked layer in three layers of said cable, and preferably three layers of this cable all are cross-linked layers.
When said cross-linkable composition is used to prepare semiconductor layer (ground floor and/or the 3rd layer); Said cross-linkable composition also comprises at least a (on the electricity) conductive filler or a kind of semiconductor fills, and its content becomes semi-conductive amount for enough making said cross-linkable composition.
More particularly, conductance is 0.001S.m at least
-1The layer of (Siemens/rice) is regarded as semiconductor layer.
Be used to obtain the cross-linkable composition of semiconductor layer, can comprise (on the electricity) conductive filler of 0.1wt%-40wt%, the preferred conductive filler of 15wt% at least, and the more preferably conductive filler of 25wt% at least.
Said semiconductor fills (conductive filler) can advantageously be selected from carbon black, CNT and graphite, or its mixture.
No matter it is first semiconductor layer, second electric insulation layer and/or the 3rd semiconductor layer, in these three layers at least one deck be extruding layer, preferably wherein two layers are extruding layer, and more preferably these three layers are extruding layer.
In a specific embodiment, the well-known cable in the application according to the present invention is formed three-layer insulated layer by first semiconductor layer, second electric insulation layer and the 3rd semiconductor layer usually.In other words, second electric insulation layer is directly to contact with the first semiconductor layer physics, and the 3rd semiconductor layer directly contacts with the second electric insulation layer physics.
Cable of the present invention can also comprise the metal protection layer that wraps up the 3rd semiconductor layer.
This metal protection layer can be " electric wire " overcoat; By be set to around and constitute along the copper or the aluminium conductor assembly of the 3rd semiconductor layer; Or " band shape " overcoat; Form around the conductive metal band of the 3rd semiconductor layer by one or more spirals that are arranged as, or " sealing " overcoat for example wraps up the metal tube of the 3rd semiconductor layer.This type overcoat especially can form obstruct from the moisture that radially infiltrates cable to tending to.
All types of metal protection layers all can serve as earth cable, thereby can conduct fault current, for example in the electrical network of being paid close attention to, occur in the situation of short circuit.
In addition, cable of the present invention can comprise the outer protection cover that wraps up the 3rd semiconductor layer, the outer protection cover of the said metal protection layer of parcel (when it exists) of perhaps saying so more specifically.This outer protection cover usually can by suitable thermoplastic for example HDPE, MDPE or LLDPE make, perhaps the material by propagation of flame retardance material or opposing flame propagation makes.Particularly, if the latter material is not contained halogen, this sheath just is considered to HFFR type (halogen-free flame retardants).
Other layer; Dilatable layer in the presence of moisture for example; Can join between the 3rd semiconductor layer and the metal protection layer (when it exists), and/or between metal protection layer and the oversheath (when they exist), above-mentioned layer provides cable vertically and/or transversely to the sealing of water.The electric conductor of cable according to the invention also can be included in dilatable material under the moisture existence and obtain " sealing sandwich layer ".
Brief description of drawings
Fig. 1 demonstrates according to the perspective of the cable of a preferred embodiment of the present invention and cross sectional representation.
Embodiment
Description in conjunction with a limiting examples of cable according to the invention presents other characteristic of the present invention and advantage, and with reference to Fig. 1, it illustrates according to the perspective of the cable of a preferred embodiment of the present invention and cross sectional representation.
Considering from clearness, only will show with diagram method understanding the indispensable key element of the present invention, is not to draw in proportion.
Medium-pressure or high pressure power cable 1 shown in Figure 1 comprises the center conductive body 2 of elongation, is mainly processed by copper or aluminium.Also coaxial successively around this electric conductor 2; This power cable 1 also comprises the metal protection layer 6 and the outer protection cover 7 of first semiconductor layer 3 (i.e. " internal semiconductive layer "), second electric insulation layer 4, the 3rd semiconductor layer 5 (promptly said " outside semiconductive layer "), ground connection and/or protectiveness, and its middle level 3,4 and 5 can be obtained by composition of the present invention.Layer 3,4 and 5 is extrude and crosslinked layer.
This construction of cable itself is well known to those skilled in the art, preferably has metal protection layer 6 and protection oversheath 7, but not necessarily.
Embodiment
The preparation of cross-linkable composition
Table 1
| Cross-linkable composition | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Polyolefin | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| BCP | 1.42 | 1.27 | 1.12 | - | - | - | - | - | - |
| DTBH | - | - | - | 1.25 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 |
| Antioxidant | 0.18 | 0.18 | 0.18 | 0.18 | 0.18 | 0.18 | 0.18 | 0.18 | 0.18 |
| TVCH | - | 1.00 | - | - | - | 1.00 | 2.00 | - | - |
| DVB | - | - | 1.00 | - | - | - | - | - | - |
| MDIB | - | - | - | - | - | - | - | 1.00 | 2.00 |
In table 1, cross-linkable composition C1, C4, C5, C8 and C9 are the comparative example, and composition C2, C3, C6 and C7 are composition of the present invention.
Each components contents of composition C1-C9 is to represent with the weight portion (pcr) with respect to the polymer of per 100 weight portions in the said cross-linkable composition, sees table 1 for details.
Details are as follows in the source of each component of composition C1-C9 in the table 1:
-" polyolefin " is that the model that In é os company sells is the low density polyethylene (LDPE) of BPD 2000;
-" BCP " is that the model that Arkema company sells is the tert-butyl peroxide isopropylbenzene (tert-butylcumyl peroxide) of Luperox 801;
-" DTBH " is that the model that Arkema company sells is 1 of Luperox 101,1-bis(t-butylperoxy) cyclohexane (aliphatic peroxides of two tertiary alkyls);
-" TVCH " is that the model that BASF AG sells is the crosslinking coagent 1,2 of TVCH, and 4-trivinyl cyclohexane (1,2,4-tri-vinylcyclohexane);
-" DVB " is that the model that Sigma-Aldrich company sells is the crosslinking coagent divinylbenzene (divinyl-benzene) of divinylbenzene; And
-" MDIB " is that the model that Sigma-Aldrich company sells is 1, between the auxiliary agent of 3-di isopropenylbenzene-and diisopropyl alkene benzene (m-diisopropenylbenzene) very.
Said composition C1-C9 is through with polyethylene pellet and each additive for example peroxide, antioxidant and optional adjuvants; Placing vapor tight tank on the mixing roll mill (ro1l mixer) to mix preparation in 3 hours, so fully this polyethylene pellet of dipping.This polyethylene pellet was preheating to 60 ℃ earlier before dipping.
Then, with said mixture at 40 ℃ of held 16 hours, hermetically storing then.
The sign of composition
The sign of non-crosslinked substrate
The crosslinked dynamics and the degree of cross linking
MDR flow graph (Moving Die Rheometer, Alpha Technologies) can be monitored the crosslinked/sulfuration (DIN 53529 (1983)) of material through the variation of measuring viscosity of material.
The chamber that holds sample is formed by two heating plates.Following plate revolves the vibration that adds constant frequency (100 cycles/minute, i.e. 1.67Hz), and amplitude is ± 0.5 ° a radian; Top plate is measured the response of material, and promptly it is to the resistance of applied stress.Unit of measurement is a moment of torsion, representes with dN.m.
Sample is prepared by the polyethylene pellet through dipping, under 120 ℃ temperature, in hydraulic press, is molded as the substrate of 3mm thickness, and according to the following cycle: not having pressure following 2 minutes was following 3 minutes of 100 bar pressures then, then cooling.
Utilize card punch from said substrate, to cut out two diameters and be used for this chamber of complete liner for the disk of 35mm; Then said disk is placed between two
polyester sheets, be placed in this flow graph chamber.
Measurement is carried out under 190 ℃ of temperature, and this is typical pipeline conditions of vulcanization.Initial decline appearred in moment of torsion owing to the fusing in advance of material after, the viscosity of material increased with the moment of torsion that is produced, and this is that crosslinked signal takes place.
The parameter of being concerned about is MH, and it measures moment of torsion corresponding to maximum.When whole system reaction back and when reaching the accessible maximum degree of cross linking, MH is a stationary value.For given material, with the good correlation of record MH and crosslink density, this has determined the thermomechanical property after the cross-linking step.
Breakdown time
Mooney's viscosimeter (Mooney viscometer, Monsanto MV2000) can be measured the viscosity of material, perhaps, for crosslinkable material, can monitor material along with change of time (standard A STM D1646 (2005)).
Mooney's viscosimeter is made up of two jaws (jaw), and above-mentioned jaw forms the cylindrical chamber of placing specimen.A metal disk with the rotation of 2rpm constant speed is contained at this chamber center.At this, use " greatly " rotor in two existing standard rotors.
In measurement, said jaw and chamber keep the temperature of pressured state and 130 ℃.
Sample is prepared by the polyethylene pellet through dipping, under 120 ℃ temperature, in hydraulic press, is molded as the substrate of 3mm thickness, and according to the following cycle: not having pressure following 2 minutes was following 3 minutes of 100 bar pressures then, then cooling.
Utilize card punch from said substrate, to cut out the disk of 4 diameters for 50mm.Wherein two disks be positioned at rotor below, its center is drilled with the hole that diameter is 12mm, so that they are through on the rotor shaft; Two other disk is intact and place it in above the rotor.Then; Integral body is placed between two
polyester sheets, put in the viscosimeter chamber.
What measure is the resistance of material to the rotor rotation.Special-purpose unit representation is used in said measurement, and Mooney (Mooney, MU).The parameter of being concerned about is: ML, the minimal viscosity value that when t0 (min), records; ML+1, this viscosity number is corresponding to the ML that increases a mooney unit, and it is measured when t1 (min); ML+2, this value is corresponding to the ML that increases by two mooney units, and it is measured when t2 (min).
According to Sievert commercial measurement volatile matter (namely for methane)
Through the Sievert method, (HY-ENERGY, SETARAM) measuring the polyethylene crosslinking stage generates the volatile matter of desorption then to use PCT Pro 2000.
Sample is prepared by the polyethylene pellet through dipping, under 120 ℃ temperature, in hydraulic press, is molded as the substrate of 1mm thickness, and according to the following cycle: not having pressure following 2 minutes was following 3 minutes of 100 bar pressures then, then cooling.
Then, utilize card punch from said substrate, to cut out the disk of diameter, weigh again, be accurate to 1mg (gross mass=300-350mg) for 6mm.
Sample is placed in the chamber of equipment, and is under pressurized (helium) state.This chamber is connected to the holder of 5ml through valve, and this holder also is under the pressured state itself.When on-test, this chamber is identical with pressure in the holder.In the temperature cycles process, this valve cycle property ground opens and closes, and when it is opened, can set up a new balance, when it is closed, measures the new air pressure in this holder then.The variation of this air pressure, part are that the release by methane causes, part is that the variation by this temperature lower chambers size causes.Therefore, reading the methane burst size in real time requires to carry out precorrection through the temperature cycles that makes this chamber experience above-mentioned design.
This equipment provides the controlled temperature linear change of 1 ℃/s, the crosslinked condition of different polyethylene layers in the simulated sulfuration pipeline.
This cycle sets is for to be heated to 250 ℃ from room temperature.
Poor through final barometric surveying value and initial gas pressure measured value under the uniform temp obtains the burst size of methane.The amount of volatile matter (namely for methane) is represented with μ mol/g crosslinked polyethylene.
The sign of crosslinked substrate
Through measuring the crosslink density that thermal creep obtains
The substrate of thickness 1mm is to be obtained by the polyethylene pellet moulding that floods.Said moulding is in press, to carry out according to the following cycle under 120 ℃: not having under the pressure 2 minutes was under 100 bar pressures 3 minutes then.Under 100 bar pressures, cool off substrate then.
Cross-linking step is carried out in press, under 190 ℃ of temperature and pressure 100 crust, continues 10 minutes.Said moulded work is preheating to 190 ℃.Remain under the pressure of 100 crust, carry out cooling step.
Measure material thermal creep amount under mechanical stress according to standard NF EN 60811-2-1.
This test is commonly referred to hot elongation test, and (Hot Set Test HST), comprising: be equivalent to apply the quality of 0.2MPa stress in an end load of H2 dumbbell shape sample, and said assembly is placed on is heated to 200 ± 1 ℃ in the baking oven and continues 15 minutes.
Afterwards, the maximum heat percentage elongation of record sample under stress is expressed as a%.
Remove sprung mass then, this sample was kept 5 minutes in baking oven again.
Measure the residue permanent elongation again, have another name called surplus ratio (or residual elongation rate), represent with a%.
Should be pointed out that crosslinked many more of material, the maximum elongation rate under the stress and the value of surplus ratio are just more little.
In addition, it is to be noted,, think in logic that then this result of the test fails under said mechanical stress and temperature acting in conjunction if sample ruptured in should test.
If percentage elongation is no more than 100%, just think that it meets the requirements, this is that the present invention is concerned about.Exceed this numerical value, be regarded as fracture equally, just think that this test behavior is undesirable.
Mechanical performance and heat aging performance
Use the pellet that floods to be molded as the substrate of 1mm thickness.This moulding process carries out in press under 120 ℃, and experiencing one, not have pressure following 2 minutes be the following 3 minutes cycles of 100 bar pressures then.Under 100 bar pressures, cool off substrate then.
Cross-linking step is carried out in press, under 190 ℃ of temperature and pressure 100 crust, continues 10 minutes.Said moulded work is preheating to 190 ℃.Remain under the pressure of 100 crust, carry out cooling step.
According to standard NF EN 60811-1-1, measure the mechanical performance (stress and elongation at break) of H2 dumbbell shape sample.
The accurate thickness of measuring samples after sample at room temperature placed 16 hours at least, makes an experiment again.Hauling speed is 200mm/min.So measure the initial mechanical performance number.
Accurately the thickness of measuring samples is put into sample in the baking oven, quickens heat ageing (following 7 days at 135 ℃), with same method sample is characterized then.So measure the variation of stress and elongation at break.No matter be tensile stress or elongation at break, when its variation be in+25% to-25% between the time, think that then this variation is satisfactory.
The non-crosslinked substrate that makes about cross-linkable composition C1-C9 and the characterization result of crosslinked substrate all are listed in the following table 2.
Table 2
The adding of auxiliary agent according to the invention can be in the crosslink density that keeps wanting to obtain, and reduces the amount of crosslinked required peroxide significantly, thereby reduces the burst size of volatile matter (methane).This is to draw according to MH and percentage elongation under in the hot elongation test 200 ℃.
The comparative example's of composition C1 (1.42pcr BCP) and C4 (1.25pcr DTBH) MH is at the order of magnitude of 3.0-3.2dN.m, and the HST percentage elongation is in the scope of 60-80%.
With regard to tert-butyl peroxide isopropylbenzene (BCP), the TVCH that adds 1.0pcr can make the amount of peroxide be reduced to 1.27pcr (composition C2), and the performance of mentioning before not influencing.Identical conclusion is applicable to the DVB among the composition C3, and for composition C3, the DVB that adds 1.0pcr can make the amount of peroxide reduce to 1.12pcr.Simultaneously, the methane content that discharges in crosslinked reduces to 101 μ mol/g XLPE (TVCH) from 113, or to 93 μ mol/g XLPE (DVB).With respect to composition C1, t1 breakdown time of composition C2, t2 and the heat aging performance under 135 ℃ all are improved.
With regard to aliphatic peroxide (DTBH), with respect to comparative example C4, the TVCH that adds 1.0pcr (composition C6) or 2.0pcr (composition C7) can make the amount of peroxide be reduced to 1.05pcr, and does not influence cross-linking properties.The methane content that discharges in crosslinked greatly reduces, and reduces to 69 μ mol/g XLPE (composition C6) or to 67 μ mol/g XLPE (composition C7) from 104.In this case, also greatly improved heat aging performance under breakdown time and 135 ℃.
The minimizing that does not add auxiliary agent (composition C5) can form cross-linking system (in HST test cleaved).
Under identical condition (1.0pcr TVCH-composition C8 and 2.0pcr TVCH-composition C9), between use-di isopropenylbenzene (MDIB) can not form full cross-linked network structure and through HST test.
Claims (12)
1. cable (1); The 3rd semiconductor layer (5) that it comprises electric conductor (2), wraps up first semiconductor layer (3) of this electric conductor (2), wraps up second electric insulation layer (4) of this ground floor (3) and wrap up this second layer (4); Above-mentioned three layer (3; 4,5) at least one deck be the cross-linked layer that obtains by cross-linkable composition, said cross-linkable composition comprises at least a polyolefin and as the organic peroxide of crosslinking agent; It is characterized in that: said composition also comprises the crosslinking coagent that contains at least two unsaturated bonds, and one of them unsaturated bond is a vinyl-functional.
2. according to the cable of claim 1, it is characterized in that at least two unsaturated bonds of said crosslinking coagent are vinyl-functional.
3. according to the cable of claim 1 or 2, it is characterized in that said polyolefin is an ethene polymers.
4. according to the cable of claim 3, it is characterized in that said ethene polymers is low density polyethylene (LDPE) (LDPE).
5. according to each cable in the aforementioned claim, it is characterized in that said cross-linkable composition comprises the polyolefin greater than 50.0 weight portions, for the polymer of per 100 weight portions in the composition.
6. according to each cable in the aforementioned claim, it is characterized in that said organic peroxide is an aliphatic peroxide.
7. according to the cable of claim 6, it is characterized in that said organic peroxide is the aliphatic peroxide of two tertiary alkyls.
8. according to each cable in the aforementioned claim, it is characterized in that said cross-linkable composition also comprises and contains at least one armaticity nuclear and the aromatic compounds that can be grafted to the single reaction property functional group on the said polyolefin.
9. according to Claim 8 cable is characterized in that the single reaction property functional group of said aromatic compounds is a vinyl-functional.
10. according to each cable in the aforementioned claim, it is characterized in that said cross-linked layer is an electric insulation layer.
11., it is characterized in that three layers of said cable all are cross-linked layers according to each cable in the aforementioned claim.
12., it is characterized in that the vinyl-functional of said crosslinking coagent is CH according to each cable in the aforementioned claim
2The olefmic functionality of=CH-type.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1151893 | 2011-03-08 | ||
| FR1151893A FR2972560A1 (en) | 2011-03-08 | 2011-03-08 | ELECTRICAL CABLE WITH MEDIUM OR HIGH VOLTAGE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102682905A true CN102682905A (en) | 2012-09-19 |
| CN102682905B CN102682905B (en) | 2016-09-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210112655.9A Expired - Fee Related CN102682905B (en) | 2011-03-08 | 2012-03-08 | Medium-pressure or high pressure cable |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2498262B1 (en) |
| KR (2) | KR20120103497A (en) |
| CN (1) | CN102682905B (en) |
| AU (1) | AU2012201176A1 (en) |
| FR (1) | FR2972560A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018090940A1 (en) * | 2016-11-16 | 2018-05-24 | Dow Global Technologies Llc | Composition with balance of dissipation factor and additive acceptance |
| CN110692112A (en) * | 2017-05-31 | 2020-01-14 | Ls电线有限公司 | Ultra-high voltage direct current power cable |
| CN110709946A (en) * | 2017-05-31 | 2020-01-17 | Ls电线有限公司 | Intermediate connection system of ultra-high voltage direct current power cable |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104284935B (en) * | 2012-05-10 | 2018-05-18 | 陶氏环球技术有限责任公司 | The ethene polymers conducting paints prepared using polybutadiene cross linking co-agents |
| FR2995313B1 (en) | 2012-09-12 | 2015-08-21 | Arkema France | PRIMARY MIXTURE OF INITIATOR AND PROMOTER OF CROSSLINK |
| CN105247628B (en) | 2013-01-31 | 2018-07-31 | Abb Hv电缆瑞士有限责任公司 | Manufacture the method in the electric high-voltage DC terminals to be insulated or connector |
| EP3298075A4 (en) | 2015-05-22 | 2019-01-23 | Dow Global Technologies LLC | Processes for preparing cables with crosslinked insulation layer and cables for same |
| WO2018221804A1 (en) * | 2017-05-31 | 2018-12-06 | 엘에스전선 주식회사 | Intermediate connection system for ultra-high-voltage direct current power cable |
| KR102256351B1 (en) * | 2017-05-31 | 2021-05-26 | 엘에스전선 주식회사 | High Voltage direct current power cable |
| WO2018221802A1 (en) * | 2017-05-31 | 2018-12-06 | 엘에스전선 주식회사 | Ultra-high voltage direct current power cable |
| WO2018221803A1 (en) * | 2017-05-31 | 2018-12-06 | 엘에스전선 주식회사 | Ultra-high voltage direct current power cable |
| IT201900004699A1 (en) * | 2019-03-29 | 2020-09-29 | Prysmian Spa | Cable with semi-conducting outermost layer |
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- 2012-03-08 CN CN201210112655.9A patent/CN102682905B/en not_active Expired - Fee Related
- 2012-03-08 EP EP12158589.7A patent/EP2498262B1/en active Active
- 2012-03-08 KR KR1020120024134A patent/KR20120103497A/en active Search and Examination
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018090940A1 (en) * | 2016-11-16 | 2018-05-24 | Dow Global Technologies Llc | Composition with balance of dissipation factor and additive acceptance |
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| CN110692112A (en) * | 2017-05-31 | 2020-01-14 | Ls电线有限公司 | Ultra-high voltage direct current power cable |
| CN110709946A (en) * | 2017-05-31 | 2020-01-17 | Ls电线有限公司 | Intermediate connection system of ultra-high voltage direct current power cable |
| CN110709946B (en) * | 2017-05-31 | 2021-01-29 | Ls电线有限公司 | Intermediate connection system of ultra-high voltage direct current power cable |
| CN110692112B (en) * | 2017-05-31 | 2021-01-29 | Ls电线有限公司 | Ultra-high voltage direct current power cable |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20120103497A (en) | 2012-09-19 |
| KR20180078194A (en) | 2018-07-09 |
| KR102053756B1 (en) | 2019-12-09 |
| FR2972560A1 (en) | 2012-09-14 |
| EP2498262B1 (en) | 2014-09-10 |
| CN102682905B (en) | 2016-09-21 |
| AU2012201176A1 (en) | 2012-09-27 |
| EP2498262A1 (en) | 2012-09-12 |
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