CN102682905B - Medium-pressure or high pressure cable - Google Patents
Medium-pressure or high pressure cable Download PDFInfo
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- CN102682905B CN102682905B CN201210112655.9A CN201210112655A CN102682905B CN 102682905 B CN102682905 B CN 102682905B CN 201210112655 A CN201210112655 A CN 201210112655A CN 102682905 B CN102682905 B CN 102682905B
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- cross
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- linkable composition
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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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- 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
Abstract
The present invention relates to a kind of cable (1), it includes electric conductor (2), wrap up first semiconductor layer (3) of this electric conductor (2), wrap up second electric insulation layer (4) of this ground floor (3) and wrap up the 3rd semiconductor layer (5) of this second layer (4), above-mentioned three layer (3, 4, 5) in, at least one of which is the cross-linked layer obtained by cross-linkable composition, described cross-linkable composition includes at least one polyolefin and the organic peroxide as cross-linking agent, it is characterized in that: described compositions also includes the crosslinking coagent containing at least two unsaturated bond, one of them unsaturated bond is vinyl-functional.
Description
Technical field
The present invention relates to a kind of cable.This cable is generally used for middle pressure (the particularly kilovolt from 6 to 45-60) or high pressure (particularly greater than 60 kilovolts, may be up to 800 kilovolts) power cable field, but not it is applied only for this, and is no matter ac cable or the situation of direct current cables is all set up.
Background technology
Medium-pressure or high pressure power cable generally comprises: center electrical conductor and, wrap up the quasiconductor internal layer of this electric conductor, electric insulation intermediate layer and semiconducting external layer successively and coaxially, these three layers are cross-linked by technology well known to those skilled in the art.
Generally, these three cross-linked layer is by compositions based on polyethylene polymer base, and obtained by mixing organic peroxide such as dicumyl peroxide or t-butylcumylperoxide (tert butyl cumyl peroxide).During cross-linking described compositions, this kind of peroxide decomposes and generates cross-linking by-products, mainly such as methane, 1-Phenylethanone., cumyl alcohol, acetone, tert-butanol, α-methyl styrene and/or water.Above-mentioned last two by-products are to be generated by the dehydration of cumyl alcohol.
If the methane generated in cross-linking step does not remove from cross-linked layer, the explosion hazard to methane and the relevant danger of inflammability cannot be ignored.Once this cable begins to use, and this gas is likely to cause damage.When semiconducting external layer is wrapped up by metal protection layer, the structure of medium and high pressure cable is typically this situation, described gas only along this cable longitudinal diffusion until the joint of electric device (namely electric power accessory) and terminals.Therefore methane may accumulate and produce the pressure to electric power accessory, and this may cause electrical breakdown.Limiting, although being present in cable, the method that methane exists, such as heat treatment cable spreads out from cable to accelerate methane, but when insulating layer thickness, these methods are time-consuming and expensive.
Document US 5 252 676 describes a kind of three-layer insulated layer for power cable.This three-layer insulated layer is to be obtained by following compositions, and described compositions includes ethylene copolymer, organic peroxide as cross-linking agent, and the additive that such as isopropenylbenzene or derivatives thereof is this kind of.In order to reduce the gas flow of release during cross-linking agent decomposes, the suggestion of described document reduces the consumption of cross-linking agent.
But, the cross-linkable composition used in described document, while providing gratifying thermo-mechanical property after making compositions crosslinking, at the aspect of the amount reducing cross-linking by-products, and it is not optimized.
Summary of the invention
It is an object of the invention to by providing a kind of medium-pressure or high pressure cable including cross-linked layer to overcome the defect of prior art, the existence of cross-linking by-products such as methane is significantly reduced in prepared by described cross-linked layer, and optimal heat mechanical property is provided simultaneously, such as thermal creep, this is the feature that described layer appropriately cross-links.
One theme of the present invention is a kind of cable, it includes electric conductor, wrap up the first semiconductor layer of this electric conductor, wrap up the second electric insulation layer of this ground floor, and wrap up the 3rd semiconductor layer of this second layer, in above-mentioned three layers, at least one of which is the cross-linked layer obtained by cross-linkable composition, described cross-linkable composition includes at least one polyolefin and the organic peroxide as cross-linking agent, it is characterized in that: described compositions also includes the crosslinking coagent containing at least two unsaturated bond, a unsaturated bond in these two unsaturated bonds is vinyl-functional, described vinyl-functional is preferably CH2The olefmic functionality of=CH-type.
Being different from described cross-linking agent, the crosslinking coagent of the present invention is multifunctional type, because it contains at least two unsaturated bonds.
The reactive functional groups of described at least two unsaturated bonds more specifically carbon-to-carbon double bond type, first it can be grafted on described polyolefin, secondly can participate in described polyolefinic crosslinking (it is, formation of the three-dimensional network of described cross-linked polyolefin).
Described crosslinking coagent can advantageously significantly reduce the ratio of the organic peroxide being used in described cross-linkable composition, thus reduce the amount being derived from the derivative methane of the cross-linking by-products of described peroxide, keep good thermo-mechanical property such as thermal creep, and gratifying crosslinking rate simultaneously.According to standard NF EN 60811-2-1, by the maximum heat percentage elongation under stress less than 100%, preferably more than 80%, and more preferably 60%-80%, it is convenient to reflect the thermo-mechanical property of cross-linked layer of the present invention.
Preferably, using the sufficiently high auxiliary agent of boiling point, so during completing the step of described cross-linkable composition, during the step having extruded described cross-linkable composition, it will not evaporate.
nullSuch as，Described crosslinking coagent is 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-norborene、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-tetra-oxaspiro [5.5] hendecane、1，2，4-triethylene 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 described crosslinking coagent are vinyl-functional, particularly CH2The olefmic functionality of=CH-type.
In this case, described crosslinking coagent is selected from 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,4,9-the last of the ten Heavenly stems triolefin, 1,9-decadinene, 3,9-divinyl-2,4,8,10-tetra-oxaspiro [5.5] hendecane, 1,2,4-triethylene cyclohexane, 1,13-14 carbon diene, 1,15-16 carbon diene.
The concentration of described auxiliary agent is preferably limited to not destroy the expressing technique of cross-linkable composition of the present invention.Such as, described cross-linkable composition can include the crosslinking coagent of at most 3 weight portions, relative to the polymer of every 100 parts in described cross-linkable composition.The auxiliary agent of 0.5 to 2 weight portions is preferably used, relative to the polymer of every 100 parts in described cross-linkable composition.
The organic peroxide of the present invention is selected from organic peroxide well known to those skilled in the art, and no matter it is aliphatic series or aromatics peroxide.
The example of the aromatics peroxide that can be mentioned that, including dicumyl peroxide and t-butylcumylperoxide.
Aliphatic peroxide (aliphatic peroxide) can be the aliphatic peroxide comprising at least one tertiary alkyl.The example of the aliphatic peroxide that can be mentioned that includes:
-aliphatic series peroxycarbonates, such as tert-amyl peroxy carbonic acid 2-ethyl hexyl ester, tertiary pentyl-peroxidating carbonic acid 2-ethyl hexyl ester, tert-butyl hydroperoxide isobutyl carbonate propyl diester；
The aliphatic peroxide of-two tertiary alkyls, such as 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 compound, di-tert-butyl peroxide, cyclic peroxide such as 3,6,9-triethyl groups-3,6,9-trimethyl-Isosorbide-5-Nitrae, 7-tri-peroxide nonane；
-aliphatic series peroxidating acetal (peroxyacetal), such as 4,4-bis(t-butylperoxy) valeric acid butyl ester；And
-aliphatic series peroxyester, such as tert-butyl peracetate, peracetic acid tertiary pentyl ester.
Compared with aromatics peroxide, the advantage of aliphatic peroxide is during the crosslinking of described cross-linkable composition not generate cross-linking by-products cumyl alcohol (cumyl alcohol), it is thus able to significantly decrease the existence of water in described cross-linked layer, keeps good thermo-mechanical property simultaneously.
In the described aliphatic peroxide mentioned, the aliphatic peroxide of two tertiary alkyls is preferably used.Reason is, this type of peroxide can make to reach well to balance between crosslinking rate and incipient scorch (burnout) or the danger of precrosslink during realizing compositions.
Preferably, described cross-linkable composition does not comprise any aromatics peroxide, the most such as dicumyl peroxide or derivatives thereof.
The peroxide method crosslinking of the cross-linkable composition of the present invention, can carry out under heat and pressure, use curing tube the most under nitrogen pressure, and this crosslinking technological is well known to those skilled in the art.
Cross-linkable composition of the present invention can include the organic peroxide less than 2.00 weight portions, the polymer of every 100 weight portions relative in described compositions；The preferably more than organic peroxide of 1.50 weight portions, the polymer of every 100 weight portions relative in described compositions；The preferably more than organic peroxide of 1.25 weight portions, the polymer of every 100 weight portions relative in described compositions；And particularly preferably less than the organic peroxide of 1.10 weight portions, the polymer of every 100 weight portions relative in described compositions.
Described term " polyolefin " substantially generally refers to olefin homo or copolymer.It can particularly show thermoplastic polymer or elastomer.
Preferably, described olefin polymer is Alathon or ethylene copolymer.
The polyvinyl example that can be mentioned that includes: linear low density polyethylene (LLDPE), Low Density Polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) (HDPE), the copolymer (EVA) of ethylene and vinyl acetate, the copolymer (EBA) of ethylene and butyl acrylate, the copolymer (EMA) of ethylene and acrylic acid methyl ester., ethylene and the copolymer (2HEA) of acrylic acid 2-hexyl ethyl ester, ethylene and the copolymer of alpha-olefin, such as polyethylen-octene (PEO), polyethylene-butene (PEB), the copolymer (EPR) of ethylene and propylene, such as ethylene-propylene-diene terpolymer (EPDM), and their mixture.
Low Density Polyethylene (LDPE) is preferably used, because it has the good characteristic for realizing rheological characteristic, is realized especially by extrusion, and well thermo-mechanical property and electrical properties.
Described term " low-density " refers to particularly 0.910-0.940g/cm3Density, and preferably 0.910-0.930g/cm3Density, according to standard ISO 1183 (at a temperature of 23 DEG C).
Typically, described Low Density Polyethylene (LDPE) can be obtained by the polymerization process in high pressure tubular reactors or autoclave reactor.
Described cross-linkable composition can include the polyolefin more than 50.0 weight portions, the polymer (namely polymeric matrix) of every 100 weight portions relative in described compositions；The polyolefin of preferably at least 70 weight portions, the polymer of every 100 weight portions relative in described compositions；And the polyolefin of particularly preferably at least 90 weight portions, the polymer of every 100 weight portions relative in described compositions.
In a kind of particularly advantageous way, described cross-linkable composition includes the polymeric matrix being only made up of polyolefin or polyolefin blend.
Cross-linkable composition of the present invention can also include, containing at least one armaticity core (aromatic nucleus) and the aromatic compounds of single reaction functional group that can be grafted on polyolefin.Preferably, the reactive functional groups of described aromatic compounds is vinyl-functional.Therefore, compared with described crosslinking coagent, when this aromatic compounds is present in described cross-linkable composition, it is not involved in polyolefinic crosslinking.
In field of cables, this cross-linkable composition the cross-linked layer obtained has enhancing and durable performance, presents preferable water tree resistance (resistance to water treeing).More particularly, it relates to electrical breakdown withstand, especially, to the elimination ability of the space charge of accumulation in high tension cable under particularly unidirectional current.
Described aromatic compounds is selected from styrene, styrene derivative and its isomer.
The example of the styrene derivative that can be mentioned that includes the compound with general formula:
Wherein, X is hydrogen, alkyl or aryl；And R is hydrogen, alkyl or aryl.More specifically, it can be mentioned 4-methyl-2,4-diphenyl amylene (pentene) and triphenylethylene.
Within the scope of this invention, polycyclic aromatic hydrocarbon (PAH) type styrene derivative is also admissible.More specifically, it can be mentioned vinylnaphthalene such as 2-vinyl naphthalene, vinyl anthracene such as 9-vinyl anthracene or 2-vinyl anthracene and vinyl phenanthrene such as 9-vinyl are luxuriant and rich with fragrance.
These aromatic compounds are grafted on polyolefinic polymer chain, are usually at polyolefinic cross-linking stage in the presence of the tertiary alkyl aliphatic peroxide of the present invention, carry out according to free radical addition mechanism well known to those skilled in the art.
The cross-linkable composition of the present invention can also include at least one protective agent, such as antioxidant.Antioxidant can protect described compositions not by the thermal limit run in the preparation process of cable or in the use of cable.
Described antioxidant is preferably selected from:
-hindered phenolic antioxidant, such as tetramethylene (4-hydroxy group-cinnamic acid 3, 5-di-t-butyl ester) methane, 3-(3, 5-di-t-butyl-4-hydroxy-pheny) propanoic acid stearyl, 2, 2'-sulfur is for double [the propanoic acid 3-(3 of divinyl, 5-di-t-butyl-4-hydroxyphenyl) ester], 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-double (3, 5-di-t-butyl-4-hydroxy group-cinnamoyl) hydrazine, [2, double (the 3-(3 of 2'-oxamido-, 5-di-t-butyl-4-hydroxyphenyl) propionate) and 2, 2'-oxamido-pair-[3-(tert-butyl group-4-hydroxyphenyl) propionate]；
-thioether; such as 4; double (octyl group sulfidomethyl) orthoresol of 6-, double [2-methyl-4-{3-n-(C12 or C14) alkylthio group-propiono epoxide }-5-tert-butyl-phenyl] sulfide and thiobis [the 2-tert-butyl group-5-methyl-4,1-phenylene] double [3-(dodecylthio)-propionic ester]；
-sulfur type antioxidant, the double stearyl or 3 of such as 3,3'-thio-2 acid, the double dodecyl ester of 3'-thio-2 acid；
-phosphorous antioxidant, such as phosphite ester or phosphonate ester, such as three (2,4-di-t-butyl phenyl) phosphite esters or double (2,4-di-t-butyl phenyl) pentaerythritol diphosphites；And
-amine type antioxidant, the most poly-2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), the in the present compositions antioxidant of particularly preferred latter type.
TMQ can be different rank, it may be assumed that
-have " standard " level of low polymerization degree, i.e. residual monomer content more than 1wt% and residual NaCl content 100ppm to more than 800ppm (every 1/1000000th, in mass)；
-have " high polymerization degree " level of high polymerization degree, i.e. residual monomer content less than 1wt% and residual NaCl content at 100ppm to more than 800ppm；
-residual NaCl content " low-residual salt content " level less than 100ppm.
The type of stabilizer and the selection of content in described cross-linkable composition, generally with polymer during prepared by mixture and relevant by maximum temperature that extrusion is to be stood during realization on cable, and also depend on the longest exposure time at such a temperature.
Described cross-linkable composition typically can include the antioxidant of 0.1wt% to 2wt%.Preferably, when being TMQ including the antioxidant less than 0.7wt%, particularly antioxidant.
Other additive well known to those skilled in the art and/or filler can also add in the cross-linkable composition of the present invention, such as puncture delayer (breakdown retardant), processing aid such as 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 of the present invention is electric insulation layer (the namely second layer).When it is electric insulation layer, described cross-linkable composition does not comprise any (electrically) conductive filler and/or does not comprise any semiconductor fills.
More specifically, in three layers of described cable, at least two is cross-linked layer, and three layers of preferred this cable are all cross-linked layers.
When described cross-linkable composition is used for preparing semiconductor layer (ground floor and/or third layer), described cross-linkable composition also includes at least one (electrically) conductive filler or a kind of semiconductor fills, and its content is the amount enough making described cross-linkable composition become quasiconductor.
More specifically, it is at least 0.001S.m by conductivity-1The layer of (Siemens/rice) is considered as semiconductor layer.
For obtaining the cross-linkable composition of semiconductor layer, it may include (electrically) conductive filler of 0.1wt%-40wt%, the conductive filler of preferably at least 15wt%, and the conductive filler of more preferably at least 25wt%.
Described semiconductor fills (conductive filler) can be advantageously selected from white carbon black, CNT and graphite, or its mixture.
No matter it is the first semiconductor layer, the second electric insulation layer and/or the 3rd semiconductor layer, and in these three layers, at least one of which is extruding layer, and two layers are extruding layer preferably wherein, and more preferably these three layers are extruding layer.
In a specific embodiment, generally according to cable well-known in application of the present invention, the first semiconductor layer, the second electric insulation layer and the 3rd semiconductor layer form three-layer insulated layer.In other words, the second electric insulation layer is direct and the first semiconductor layer physical contact, and the 3rd semiconductor layer is direct and the second electric insulation layer physical contact.
The cable of the present invention can also include the metal protection layer wrapping up the 3rd semiconductor layer.
This metal protection layer can be " electric wire " overcoat, by being arranged around and constituting along copper or the aluminium conductor assembly of the 3rd semiconductor layer, or " banding " overcoat, it is made up of one or more conductive metal bands being arranged as spiraling about the 3rd semiconductor layer, or " sealing " overcoat such as wraps up the metal tube of the 3rd semiconductor layer.This kind of overcoat enables in particular to tending to be formed from the moisture radially penetrating into cable intercept.
All types of metal protection layers all may act as earth cable, thus can conduct fault current, such as, occur in the case of short circuit in the electrical network paid close attention to.
Additionally, the cable of the present invention can include the outer protective jacket wrapping up the 3rd semiconductor layer, or it is the outer protective jacket wrapping up described metal protection layer (in the presence of it) in particular.This outer protective jacket generally can be prepared by suitable thermoplastic such as HDPE, MDPE or LLDPE, or the material by propagation of flame retarder or to flame propagation resistant prepares.Particularly, if latter material does not contains halogen, this sheath is regarded as HFFR type (halogen-free flame retardants).
Other layer, the most dilatable layer, can join between the 3rd semiconductor layer and metal protection layer (when present), and/or between metal protection layer and oversheath (when they exist), above-mentioned layer provides the cable sealing in longitudinal and/or transverse direction to water.The electric conductor of cable of the present invention can also include that the most dilatable material obtains " sealing sandwich layer ".
The brief description of accompanying drawing
Fig. 1 demonstrates perspective and the cross sectional representation of the cable according to a preferred embodiment of the present invention.
Detailed description of the invention
In conjunction with the description of a limiting examples of cable of the present invention, present other features and advantages of the invention, with reference to Fig. 1, its perspective illustrating the cable according to a preferred embodiment of the present invention and cross sectional representation.
For clarity, only will be not necessarily drawn to scale understanding that the indispensable key element of the present invention diagrammatically shows.
Medium-pressure or high pressure power cable 1 shown in Fig. 1, including the center conductor 2 of elongation, is mainly made up of copper or aluminum.Successively and coaxially around this electric conductor 2; this power cable 1 also includes the first semiconductor layer 3 (i.e. " internal semiconductive layer "), the second electric insulation layer the 4, the 3rd semiconductor layer 5 (i.e. described " outside semiconductive layer "), ground connection and/or the metal protection layer 6 of protectiveness and outer protective jacket 7, and its middle level 3,4 and 5 can be obtained by the compositions of the present invention.Layer that is that layer 3,4 and 5 is extrusion and that cross-link.
This construction of cable itself is well known to those skilled in the art, preferably there is metal protection layer 6 and protects 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 comparative example, and compositions C2, C3, C6 and C7 are the compositions of the present invention.
The content of each component of compositions C1-C9 is that the weight portion (pcr) of the polymer with 100 weight portions every relative in described cross-linkable composition represents, refers to table 1.
In table 1, details are as follows in the source of each component of compositions C1-C9:
-" polyolefin " is the Low Density Polyethylene that model is BPD 2000 that In é os company sells；
-" BCP " is the t-butylcumylperoxide that model is Luperox 801 (tert-butylcumyl peroxide) that Arkema company sells；
-" DTBH " is model is Luperox 101 1 that Arkema company sells, 1-bis(t-butylperoxy) cyclohexane (aliphatic peroxides of two tertiary alkyls)；
-" TVCH " is the crosslinking coagent that model is TVCH 1 that BASF AG sells, 2,4-triethylene cyclohexane (1,2,4-tri-vinylcyclohexane)；
-" DVB " is crosslinking coagent divinylbenzene (divinyl-benzene) that model is divinylbenzene that Sigma-Aldrich company sells；And
-" MDIB " be Sigma-Aldrich company sell model be 1, the auxiliary agent m-diisopropyl alkene very benzene (m-diisopropenylbenzene) of 3-di isopropenylbenzene.
Described compositions C1-C9 is by by polyethylene pellet and each additive such as peroxide, antioxidant and optional auxiliary agent, in the vapor tight tank being placed on mixing roll mill (ro1l mixer), mix preparation in 3 hours, be so sufficiently impregnated with this polyethylene pellet.This polyethylene pellet is the most first preheating to 60 DEG C.
Then, described mixture is placed 16 hours at 40 DEG C, then hermetically storing.
The sign of compositions
The sign of non-crosslinked substrate
·Kinetics and the degree of cross linking
MDR flow graph (Moving Die Rheometer, Alpha Technologies) can monitor cross-linking/vulcanizing (DIN 53529 (1983)) of material by measuring the change of viscosity of material.
The chamber accommodating sample is formed by two heating plates.Following plate rotation adds the vibration of constant frequency (100 cycles/minute, i.e. 1.67Hz), and amplitude is the radian of ± 0.5 °；Plate above measures the response value of material, i.e. its resistance to applied stress.Measurement unit is moment of torsion, represents with dN.m.
Sample is prepared by the polyethylene pellet being through impregnation with, and is molded as the substrate of 3mm thickness at a temperature of 120 DEG C in hydraulic press, the cycle according to following: does not has lower 2 minutes followed by 100 bar pressures of pressure lower 3 minutes, then cools down.
Utilize card punch to cut out the disk of two a diameter of 35mm from described substrate for this chamber of complete liner, then described disk is placed in twoBetween polyester sheet, it is placed in this flow graph chamber.
Measurement is carried out at a temperature of 190 DEG C, and this is typical pipeline conditions of vulcanization.After moment of torsion occurs initially declining due to the fusing in advance of material, the viscosity of material and produced moment of torsion increase, and this is the signal crosslinked.
Parameter of interest is MH, and it measures moment of torsion corresponding to maximum.When, after whole system is reacted and when reaching the accessible maximum degree of cross linking, MH is a stationary value.For given material, by record MH and the good correlation of crosslink density, which dictates that the thermomechanical property after cross-linking step.
·Breakdown time
Mooney's viscosimeter (Mooney viscometer, Monsanto MV2000) can measure the viscosity of material, or, for crosslinkable material, it is possible to monitoring material change (standard ASTM D1646 (2005)) over time.
Mooney's viscosimeter is made up of two jaws (jaw), and above-mentioned jaw forms the cylindrical chamber placing test sample.This chamber center contains one with the metal disk of 2rpm constant speed rotary.Here, use " greatly " rotor in two existing standard rotors.
In the measurements, described jaw and chamber keep pressured state and the temperature of 130 DEG C.
Sample is prepared by the polyethylene pellet being through impregnation with, and is molded as the substrate of 3mm thickness at a temperature of 120 DEG C in hydraulic press, the cycle according to following: does not has lower 2 minutes followed by 100 bar pressures of pressure lower 3 minutes, then cools down.
Card punch is utilized to cut out the disk of 4 a diameter of 50mm from described substrate.Two of which disk is positioned at below rotor, and its center is drilled with the hole of a diameter of 12mm, so that they are through in rotor shaft；By intact for two other disk and place it in above rotor.Then, two will be integrally placed atBetween polyester sheet, put in viscometer chamber.
Measure is the material resistance that rotates rotor.Described measurement represents by special unit, Mooney (Mooney, MU).Parameter of interest is: ML, the minimal viscosity value recorded when t0 (min)；ML+1, this viscosity number is corresponding to increasing the ML of a mooney unit, and it is measured when t1 (min)；ML+2, this value is corresponding to increasing the ML of two mooney units, and it is measured when t2 (min).
·According to Sievert Commercial measurement volatile matter ( Namely for methane )
By Sievert method, PCT Pro 2000 (HY-ENERGY, SETARAM) is used to measure the volatile matter that then generation of polyethylene crosslinking stage is desorbed.
Sample is prepared by the polyethylene pellet being through impregnation with, and is molded as the substrate of 1mm thickness at a temperature of 120 DEG C in hydraulic press, the cycle according to following: does not has lower 2 minutes followed by 100 bar pressures of pressure lower 3 minutes, then cools down.
Then, utilize card punch to cut out the disk of a diameter of 6mm from described substrate, be re-weighed, be accurate to 1mg (gross mass=300-350mg).
Sample is placed in the chamber of equipment, and is under pressurized (helium) state.This chamber is connected to the bin of 5ml by valve, and this bin is also under pressured state itself.When on-test, the pressure in this chamber and bin is identical.During temperature cycles, this valve cycle ground opens and closes, and can set up a new balance when it is opened, the most when it is closed, measure the new air pressure in this bin.The change of this air pressure, part is to be caused by the release of methane, and part is to be caused by the change of chamber size at a temperature of this.Therefore, read Methane Emissions in real time to require to carry out precorrection by the temperature cycles making this chamber experience above-mentioned design.
This equipment provides the controlled temperature linear change of 1 DEG C/s, the cross linking conditions of different polyethylene layers in simulated sulfuration pipeline.
This circulation is set as being heated to 250 DEG C from room temperature.
By gas pressure measurement final at identical temperature and the difference of initial gas pressure measured value, obtain the burst size of methane.The amount μm ol/g crosslinked polyethylene of volatile matter (namely for methane) represents.
The sign of crosslinking substrate
·By measuring the crosslink density that thermal creep obtains
The substrate of thickness 1mm is to be obtained by the polyethylene pellet molding impregnated.Described molding is to carry out according to the following cycle in press at 120 DEG C: 2 minutes followed by under 100 bar pressures 3 minutes under not having pressure.Then under 100 bar pressures, cool down substrate.
Cross-linking step is carried out in press, continues 10 minutes at temperature 190 DEG C and pressure 100 bar.Described moulded work is preheating to 190 DEG C.It is maintained under the pressure of 100 bars, carries out cooling step.
Material thermal creep amount under mechanical stress is measured according to standard NF EN 60811-2-1.
This tests commonly referred to hot elongation test (Hot Set Test, HST), including: be equivalent to apply the quality of 0.2MPa stress in one end of H2 dumbbell shape sample load, and the placement of described assembly is heated to 200 ± 1 DEG C lasting 15 minutes in an oven.
Afterwards, record sample maximum heat percentage elongation under stress, be expressed as a%.
Then remove sprung mass, this sample is retained 5 minutes the most in an oven.
Measure residue permanent elongation again, have another name called surplus ratio (or residual elongation rate), represent with a%.
It should be pointed out that, crosslink material is the most, maximum elongation rate and the value of surplus ratio under stress are the least.
If further, it is noted that sample ruptures under described mechanical stress and temperature act on jointly in this test, thinking that this result of the test is failed the most in logic.
If percentage elongation is less than 100%, being considered as it and meet the requirements, this is that the present invention is of interest.Beyond this numerical value, being considered fracture equally, it is undesirable for being considered as this test behavior.
·Mechanical performance and heat aging performance
The pellet using dipping is molded as the substrate of 1mm thickness.This moulding process be at 120 DEG C in press
Carrying out, experiencing one does not has the lower 2 minutes followed by 100 bar pressure cycles of lower 3 minutes of pressure.Then under 100 bar pressures, cool down substrate.
Cross-linking step is carried out in press, continues 10 minutes at temperature 190 DEG C and pressure 100 bar.Described moulded work is preheating to 190 DEG C.It is maintained under the pressure of 100 bars, carries 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.
Accurately the thickness of measuring samples, after at room temperature sample is placed at least 16 hours, then tests.Hauling speed is 200mm/min.So measure initial mechanical performance number.
Accurately the thickness of measuring samples, puts into sample in baking oven, is accelerated heat ageing (7 days at 135 DEG C), characterizes sample the most in the same way.So measure stress and the change of elongation at break.No matter it is tensile stress or elongation at break, when its change is between+25% to-25%, then it is assumed that this change is satisfactory.
The non-crosslinked substrate prepared about cross-linkable composition C1-C9 and the characterization result of crosslinking substrate, be all listed in table 2 below.
Table 2
The addition of auxiliary agent of the present invention can significantly decrease the amount of peroxide needed for crosslinking, thus reduce the burst size of volatile matter (methane) while keeping wanting the crosslink density obtained.This is to draw according to the MH in hot elongation test 200 DEG C and percentage elongation.
The MH of the comparative example of compositions C1 (1.42pcr BCP) and C4 (1.25pcr DTBH) is at the order of magnitude of 3.0-3.2dN.m, and HST percentage elongation is in the range of 60-80%.
For t-butylcumylperoxide (BCP), the TVCH adding 1.0pcr can make the amount of peroxide be reduced to 1.27pcr (compositions C2), and does not affect the performance mentioned before.Identical conclusion DVB be applicable to compositions C3, for compositions C3, the DVB adding 1.0pcr can make the amount of peroxide be reduced to 1.12pcr.Meanwhile, in crosslinking, the methane content of release is reduced to 101 μm ol/g XLPE (TVCH) from 113, or to 93 μm ol/g XLPE (DVB).Relative to compositions C1, compositions C2 breakdown time t1, t2 and the heat aging performance at 135 DEG C be all improved.
For aliphatic peroxide (DTBH), relative to comparative example C4, the TVCH adding 1.0pcr (compositions C6) or 2.0pcr (compositions C7) can make the amount of peroxide be reduced to 1.05pcr, and does not affect cross-linking properties.In crosslinking, the methane content of release greatly reduces, and is reduced to 69 μm ol/g XLPE (compositions C6) or to 67 μm ol/g XLPE (compositions C7) from 104.In this case, the heat aging performance at breakdown time and 135 DEG C is also significantly improved.
The minimizing being added without auxiliary agent (compositions C5) can form cross-linking system (rupturing in HST tests).
At identical conditions (1.0pcr TVCH-compositions C8 and 2.0pcr TVCH-compositions C9), m-di isopropenylbenzene (MDIB) is used full cross-linked network structure will not to be formed and tested by HST.
Claims (13)
1. cable (1), it includes electric conductor (2), the first semiconductor layer (3) wrapping up this electric conductor (2), bag
Wrap up in second electric insulation layer (4) of this ground floor (3) and wrap up the 3rd semiconductor layer (5) of this second layer (4),
In above-mentioned three layers (3,4,5), at least one of which is the cross-linked layer obtained by cross-linkable composition, described cross-linking group
Compound includes at least one polyolefin and the organic peroxide as cross-linking agent, it is characterised in that: described
Compositions also includes the crosslinking coagent containing at least two unsaturated bond, in these two unsaturated bonds
Unsaturated bond is CH2The vinyl-functional of=CH-type, and two of wherein said crosslinking coagent are not
First saturated bond can be grafted on described polyolefin, secondly can participate in described polyolefinic crosslinking.
Cable the most according to claim 1, it is characterised in that at least two insatiable hunger of described crosslinking coagent
It is vinyl-functional with key.
Cable the most according to claim 1, it is characterised in that described polyolefin is ethene polymers.
Cable the most according to claim 3, it is characterised in that described ethene polymers is low density polyethylene
Alkene (LDPE).
Cable the most according to claim 1, it is characterised in that described cross-linkable composition includes being more than
The polyolefin of 50.0 weight portions, for the polymer of 100 weight portions every in compositions.
Cable the most according to claim 1, it is characterised in that described organic peroxide is aliphatic series peroxide
Compound.
Cable the most according to claim 6, it is characterised in that described organic peroxide is two tertiary alkyls
Aliphatic peroxide.
Cable the most according to claim 1, it is characterised in that described cross-linkable composition also include containing
At least one armaticity core and the aromatics of single reaction functional group can being grafted on described polyolefin
Compound.
Cable the most according to claim 8, it is characterised in that the single reaction official of described aromatic compounds
Can group be vinyl-functional.
Cable the most according to claim 1, it is characterised in that described cross-linked layer is electric insulation layer.
11. cables according to claim 1, it is characterised in that three layers (3,4,5) of described cable are all
It it is cross-linked layer.
12. cables according to claim 1, it is characterised in that described cross-linkable composition includes at most
The crosslinking coagent of 3 weight portions, relative to the polymer of every 100 parts in described cross-linkable composition.
13. cables according to claim 1, it is characterised in that described crosslinking coagent is non-polymeric.
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 CN102682905A (en) | 2012-09-19 |
| CN102682905B true 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) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2847266B1 (en) * | 2012-05-10 | 2019-03-13 | Dow Global Technologies LLC | Ethylene polymer conductor coatings prepared with polybutadiene cross-linking coagents |
| FR2995313B1 (en) | 2012-09-12 | 2015-08-21 | Arkema France | PRIMARY MIXTURE OF INITIATOR AND PROMOTER OF CROSSLINK |
| WO2014117841A1 (en) * | 2013-01-31 | 2014-08-07 | Abb Technology Ltd | Method in the manufacturing of an insulated electric high voltage dc termination or joint |
| WO2016187755A1 (en) | 2015-05-22 | 2016-12-01 | Dow Global Technologies Llc | Processes for preparing cables with crosslinked insulation layer and cables for same |
| CN109963902B (en) * | 2016-11-16 | 2022-04-15 | 陶氏环球技术有限责任公司 | Composition with balanced dissipation factor and additive receptivity |
| WO2018221802A1 (en) * | 2017-05-31 | 2018-12-06 | 엘에스전선 주식회사 | Ultra-high voltage direct current power cable |
| KR102499648B1 (en) | 2017-05-31 | 2023-02-14 | 엘에스전선 주식회사 | High voltage DC power cable joint system |
| WO2018221803A1 (en) * | 2017-05-31 | 2018-12-06 | 엘에스전선 주식회사 | Ultra-high voltage direct current power cable |
| KR102256351B1 (en) * | 2017-05-31 | 2021-05-26 | 엘에스전선 주식회사 | High Voltage direct current power cable |
| KR102256323B1 (en) * | 2017-05-31 | 2021-05-26 | 엘에스전선 주식회사 | High Voltage direct current power cable |
| WO2018221804A1 (en) * | 2017-05-31 | 2018-12-06 | 엘에스전선 주식회사 | Intermediate connection system for 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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-
2011
- 2011-03-08 FR FR1151893A patent/FR2972560A1/en not_active Withdrawn
-
2012
- 2012-02-28 AU AU2012201176A patent/AU2012201176A1/en not_active Abandoned
- 2012-03-08 CN CN201210112655.9A patent/CN102682905B/en not_active Expired - Fee Related
- 2012-03-08 KR KR1020120024134A patent/KR20120103497A/en active Search and Examination
- 2012-03-08 EP EP12158589.7A patent/EP2498262B1/en active Active
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2018
- 2018-06-27 KR KR1020180073836A patent/KR102053756B1/en active IP Right Grant
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| CN88100263A (en) * | 1987-01-26 | 1988-08-10 | 利森蒂亚专利管理有限公司 | Plastic insulation material |
| EP0579434A1 (en) * | 1992-07-16 | 1994-01-19 | Nof Corporation | Dialkyl peroxide, cross-linking composition containing the same, method for cross-linking, and electric power cable |
| EP1156493A1 (en) * | 2000-05-19 | 2001-11-21 | Sagem Sa | Crosslinkable semi-conductive composition and electrical cable with semi-conductive film |
| CN101146859A (en) * | 2006-02-24 | 2008-03-19 | Lg化学株式会社 | Cross-linked polyethylene having excellent inhibition of sweat-out and insulation properties |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20180078194A (en) | 2018-07-09 |
| CN102682905A (en) | 2012-09-19 |
| KR102053756B1 (en) | 2019-12-09 |
| EP2498262A1 (en) | 2012-09-12 |
| KR20120103497A (en) | 2012-09-19 |
| FR2972560A1 (en) | 2012-09-14 |
| AU2012201176A1 (en) | 2012-09-27 |
| EP2498262B1 (en) | 2014-09-10 |
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